Cassia Derivatives

ABSTRACT

This invention related to a cationically and hydrophilically modified polygalactomannan having repeating units with an average D-mannosyl to D-galactosyl residue ratio of at least 5 to 1 and to compositions containing the same. A portion of the hydrogen atoms of hydroxyl groups situated on the mannosyl and galactosyl residues of the galactomannan are replaced with a hydrophilic and a cationic substituent.

TECHNICAL FIELD

This invention generally relates to galactomannan derivatives. Morespecifically, the invention relates to cationically and hydrophilicallymodified galactomannan polymers obtained from the endosperm of seedsobtained from the plant genus Cassia and to their use in personal care,health care, household, institutional and industrial care compositionsand the like. The cationically and hydrophilically modified Cassiagalactomannan polymers of this invention are useful as deposition aids,stabilizers, emulsifiers, spreading aids and carriers for enhancing theefficacy, deposition and delivery of chemically and physiologicallyactive ingredients. In addition, such polymers are useful as an activecomponent in personal care compositions as film formers, hair fixatives,hair conditioners, and skin conditioners. They are also useful forimproving the psychosensory and aesthetic properties of personal careformulations in which they are included.

BACKGROUND OF THE INVENTION

Galactomannans are a class of polysaccharides that are found in theendosperm material of seeds from leguminous plants such as Cyamopsistetragonoloba (guar gum), Cesalpinia spinosa (tara gum), Ceratoniasiliqua (locust bean gum), and other members of the Leguminosae family.A galactomannan is composed of backbone of 1→4-linked β-D-mannopyranosylmain chain units (also designated herein as a mannoside unit or residue)with recurring 1→6-linked α-D-galactosyl side groups (also designatedherein as a galactoside unit or residue) branching from the number 6carbon atom of a mannopyranose residue in the polymer backbone. Thegalactomannan polymers of the different Leguminosae species differ fromone another in the frequency of the occurrence of the galactoside sideunits branching from the polymannoside backbone. The mannoside andgalactoside units are generically referred to herein as glycoside unitsor residues. The average ratio of D-mannoside to D-galactoside units inthe galactomannan contained in guar gum is approximately 1.5 or 2:1,approximately 3:1 for tara gum, and approximately 4:1 for locust beangum. Another important source of polygalactomannan is isolated from theendosperm of seeds of Cassia tora and Cassia obtusifolia (known ascassia gum). Cassia gum has an average ratio of mannose to galactose ofat least 5:1. For illustrative purposes galactomannans obtained from theendosperm of cassia seed can be schematically represented by thestructure:

wherein n is an integer representing the number of repeat units in thepolymer. The polygalactomannan used in the practice of this inventiontypically has a weight average molecular weight (Mw) which is within therange of 200,000 to 5,000,000 Daltons. In many cases, thepolygalactomannan has a weight average molecular weight, which is withinthe range of 300,000 to 2,000,000 Daltons. It is common for thegalactomannan used in the practice of this invention to have a weightaverage molecular weight, which is within the range of 400,000 to1,500,000 Daltons. The molecular weight of the galactomannan can bevaried through controlled degradation procedures known in the art.

The underivatized Cassia galactomannan used as a starting material inthe practice of this invention typically has a number average molecularweight (Mn) which is within the range of 100,000 to 1,500,000 Daltons.In many cases, the polygalactomannan has a number average molecularweight, which is within the range of 200,000 to 1,000,000 Daltons. In iscommon for the polygalactomannan used in the practice of this inventionto have a number average molecular weight, which is within the range of300,000 to 800,000 Daltons.

Galactomannans are hydrocolloids that have a high affinity for water.They have been widely used as, thickening, emulsifying, and gellingagents in applications as diverse as foodstuffs, coatings, personal carecompositions and in oil well fracturing fluids. Although the use ofthese polymers has been met with great success, galactomannans used intheir natural form have suffered some drawbacks from a water solubilitystandpoint. An unsubstituted polymannose backbone is completelyinsoluble in water. The attachment of galactose side units to the C-6atom in the recurring mannose residues of the polymannose backboneincreases the water solubility of the polymer, particularly in coldwater (i.e., ambient temperature and below). The greater the galactoseside unit substitution, the greater is the cold water solubilityproperties of the polygalactomannan. Consequently, lower ratios ofD-mannosyl to D-galactosyl units in the polygalactomannan leads tobetter cold water solubility. For example, the polygalactomannancontained in guar gum (average D-mannosyl to D-galactosyl ratio 2:1) ismostly soluble in cold water, while the polygalactomannan obtained fromcassia gum (average D-mannosyl to D-galactosyl ratio of at least 5:1) isonly sparingly soluble in cold and hot water.

U.S. Pat. No. 4,753,659 to Bayerlein et al. discloses inter alia thatimproved cold water solubility can be imparted to cassia gum bychemically modifying the polygalactomannan. The reaction of cassia gumpolygalactomannan with selected reagents to yield derivatized Cassia isdisclosed. Exemplary reaction products include substituted andunsubstituted alkyl ethers, substituted phosphate esters, andsubstituted quaternary ammonium derivatives. Disclosed uses for thechemically modified cassia gum polygalactomannans include textileprinting applications, oil well drilling auxiliaries, mining andexplosives applications.

U.S. Pat. No. 7,262,157 to Utz et al. discloses a personal carecomposition comprising a Cassia galactomannan polymer having repeatingunits containing a D-mannosyl to D-galactosyl residue ratio of 5 to 1wherein a portion of the hydrogen groups on the pendant hydroxysubstituents on the mannosyl and galactosyl residues are substitutedwith a group represented by the formula: AR¹ wherein A is a substitutedor unsubstituted alkylene group containing 1 to 6 carbon atoms, and R¹is a group independently selected from —N⁺(R³)₃X⁻, —S⁺(R³)₂X⁻, and—P⁺(R³)₃X⁻, wherein R³ independently represents substituted andunsubstituted C₁-C₂₄ alkyl, substituted and unsubstituted benzyl andsubstituted and unsubstituted phenyl; and X is any suitable anion thatbalances the charge on the onium cation.

In personal care, health care, household care, and institutional andindustrial care applications the solubility characteristics of activeingredients and formulation aids in aqueous systems are of paramountimportance. While the cationically derivatized Cassia galactomannansdisclosed in U.S. Pat. No. 7,262,157 are soluble in aqueous basedformulations, a relatively high degree of cationic substitution isneeded to achieve useful properties. There is a need to providecationically derivatized Cassia galactomannans that exhibit cationicsubstantivity across a wide range of substitution levels as well andother properties significant for personal care, health care, householdcare, and institutional and industrial care applications while retainingsignificant water solubility. Additionally, there is a need for acationically and hydrophilically modified galactomannan polymer thatimparts significantly better sensory performance in personal care andhealth care applications. Such galactomannans would have widespreadutility in applications not heretofore obtained in the prior art.

SUMMARY OF THE INVENTION

The present invention concerns a cationically and hydrophilicallymodified galactomannan having an average mannose to galactose ratio ofat least 5:1 wherein a portion or all of the hydrogen atoms of thehydroxyl groups present on the galactomannan are independentlysubstituted with at least one cationic moiety represented by formula (I)and at least one hydrophilic moiety that contains a polyoxyalkylenegroup as set forth in formula (II) below.

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical, and whensubstituted said substituent, independently, is selected from hydroxyland halo; R, independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and—P⁺R³R⁴R⁵X⁻, wherein R³ and R⁴, and R⁵, independently, are selected fromhydrogen and linear and branched C₁-C₂₄ alkyl, and X⁻represents ananion; (R¹—O)_(c) represents a oxyalkylene moiety or a polyoxyalkylenemoiety arranged as a homopolymer, a random copolymer or a blockcopolymer of oxyalkylene units, wherein R¹, independently, is selectedfrom linear and branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups,and c is an integer ranging from about 1 to about 250 in one aspect,from about 2 to about 200 in another aspect, from about 2 to about 150in still another aspect, from about 5 to about 100 in a further aspect,and from about 10 to about 50 in a still further aspect and; R²,independently, is selected from hydrogen, methyl, and AR; and a is 0 or1; b is 0 or 1, subject to the proviso that when a is 0, b is 0, andwhen R² is AR in formula (II), the cationic moiety AR represented byformula (I) is optionally present; and when c is 1, R² is not hydrogen.As set forth above, the hydrophilic moiety depicted in formula (II) canbe terminated with a moiety selected from hydrogen (e.g., a terminalhydroxyl group), a methyl group (e.g., a terminal methoxy group), and acationic group (e.g., AR as previously defined).

The hydrophilic modification of the Cassia polygalactomannan backbonewith substituents conforming to formula (II) confers better solubilityprofiles at lower cationic substitution levels when compared tounmodified cationic Cassia and other cationically modifiedpolysaccharides. Surprisingly, the hydrophilic modification ofcationically derivatized Cassia imparts a better sensory profile interms of conditioning such as, for example, wet and dry combing of thehair and wet and dry feel of the hair.

The invention also concerns a personal care composition comprising A)the cationically and hydrophilically modified galactomannan describedabove and B) at least one ingredient selected from surfactants,emulsifiers, emollients, moisturizers, auxiliary hair and skinconditioning agents, auxiliary hair fixatives, auxiliary film-formers,skin protectants (e.g., sunscreen agents), binders, chelating agents,disinfectants, insecticides, fungicides, deodorants, pest repellants,odoriferous materials, antimicrobial agents, antifungal agents,antibiotics, antidandruff agents, abrasives, adhesives, skin anti-agingand anti-wrinkle agents, absorbents, colorants, deodorants,antiperspirant agents, humectants, opacifying and pearlescing agents,antioxidants, preservatives, propellants, spreading agents, exfoliants,keratolytic agents, blood coagulants, vitamins, artificial tanningaccelerators, pH adjusting agents, botanicals, hair colorants, oxidizingagents reducing agents, skin bleaching agents, pigments,anti-inflammatory agents, topical anesthetics, fragrance and fragrancesolubilizers, particulates, microabrasives, abrasives, and combinationsthereof.

DETAILED DESCRIPTION OF THE INVENTION

Exemplary embodiments in accordance with the present invention will bedescribed. Various modifications, adaptations or variations of suchexemplary embodiments described herein may become apparent to thoseskilled in the art as such are disclosed. It will be understood that allsuch modifications, adaptations or variations that rely upon theteachings of the present invention, and through which these teachingshave advanced the art, are considered to be within the scope and spiritof the present invention.

The polymers and compositions of the present invention may suitablycomprise, consist of, or consist essentially of the components,elements, and process delineations described herein. The inventionillustratively disclosed herein suitably may be practiced in the absenceof any element which is not specifically disclosed herein.

Unless otherwise stated, all percentages, parts, and ratios expressedherein are based upon weight of the total compositions of the presentinvention.

In one embodiment of the invention, the average ratio of D-mannosyl toD-galactosyl units (M:G units) in the polygalactomannan contained inCassia endosperm is at least 5:1. In another embodiment, the averageratio of M:G units ranges from about 5:1 to about 49:1 in one aspect,from about 5:1 to about 35:1 in another aspect, from about 5:1 to about25:1 in still another aspect, from about 5:1 to about 10:1 in a furtheraspect, and about 5:1, about 6:1, about 7:1, or about 8:1 in otheraspects of the invention. In another embodiment, the Cassia gumencompassing the M:G ratios set forth above is obtained from theendosperm of Cassia tora, Cassia obtusifolia, and mixtures thereof.

In another embodiment, the amount of galactose contained in the Cassiapolygalactomannan is at least 2 wt. % based on the total amount ofmannose and galactose present in the galactomannan. In one aspect, theamount of galactose ranges from about 2 wt. % to about 17 wt. %, inanother aspect from about 3 wt. % to about 14 wt. %, in still anotheraspect from about 4 wt. % to about 13 wt. %, and in a further aspectfrom about 5 wt. % to about 11 wt. %, wherein all weights are based onthe total amount of mannose and galactose present in the galactomannan.In another embodiment, the Cassia gum encompassing the galactose weightranges set forth above is obtained from the endosperm of Cassia tora,Cassia obtusifolia, and mixtures thereof.

In one aspect, the present invention concerns a cationically andhydrophilically modified galactomannan having an average mannose togalactose ratio embracing the M:G ratios set forth above wherein aportion or all of the hydrogen atoms of the hydroxyl groups present onthe galactomannan are substituted with a least one cationic moietyrepresented by formula (I) and at least one hydrophilic moietyrepresented by formula (II) as follows:

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical in oneaspect, a divalent linear or branched, substituted or unsubstitutedC₁-C₅ alkylene radical in another aspect, a divalent linear or branched,substituted or unsubstituted C₁-C₄ alkylene radical in still anotheraspect, a divalent linear or branched, substituted or unsubstitutedC₁-C₃ alkylene radical in a further aspect, and a divalent linear,substituted or unsubstituted C₃ alkylene radical in a still furtheraspect, and when substituted said substituent, independently, isselected from hydroxyl and halo (e.g., chloro, bromo, iodo); R,independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and —P⁺R³R⁴R⁵X⁻,wherein R³ and R⁴, and R⁵, independently, are selected from hydrogen andlinear and branched C₁-C₂₄ alkyl, and X⁻ represents an anion; (R¹—O)_(c)represents a polyoxyalkylene moiety arranged as a homopolymer, a randomcopolymer or a block copolymer of oxyalkylene units, wherein R¹,independently, is selected from linear and branched C₂H₄, C₃H₆, and C₄H₈divalent alkylene groups, and c is an integer ranging from about 1 toabout 250, in one aspect, from about 2 to about 200 in another aspect,from about 2 to about 150 in still another aspect, from about 5 to about100 in a further aspect, and about 10 to about 50 in a still furtheraspect; R², independently, is selected from hydrogen, methyl, and AR;and a is 0 or 1; b is 0 or 1, subject to the proviso that when a is 0, bis 0, and when R² is AR in formula (II), the cationic moiety ARrepresented by formula (I) is optionally present; and when c is 1, R² isnot hydrogen.

In one aspect, embodiments of the present invention relate togalactomannan compositions that are hydrophilically modified (e.g.,polyalkoxylated) and cationically modified (e.g., quaternized) tomaintain solubility in aqueous media while allowing for varying degreesof cationic substitution. Theoretically, an average of 3 hydroxyl groupsreside on each unsubstituted glycoside unit in the galactomannan polymerbackbone. The hydroxyl groups on each glycoside unit can behydrophilically and/or cationically derivatized with hydrophilic andcationic moieties that are coreactive therewith. The total degree ofsubstitution (DS) (of both cationic and hydrophilic species) is 1.0 whenone hydroxyl group on each glycoside unit is derivatized, and 3.0 when,on average, 3 hydroxyl groups of each glycoside unit are derivatized.Average total DS values are shown as decimal fractions of these integervalues, and mean that the galactomannan is made up of glycoside unitshaving whole number DS values embracing the average.

The water solubility of the cationically and hydrophilically modifiedCassia galactomannan of this invention represents a balance between thehydrophilic moieties on the galactomannan, such as provided by thepolyalkoxylated containing substituents defined by formula (II) above,and the cationic moieties of the galactomannan, such as provided by thecationic substituents defined under formula (I) above. In one embodimentof the invention, a substituent on the galactomannan can contain both ahydrophilic moiety and a cationic moiety as represented by formula (II)when R² is AR as defined above. To the extent that a decreased degree ofsubstitution as defined by formula (I) (DS_(I)) limits the watersolubility of the Cassia galactomannan, a corresponding increase in thedegree of substitution of the hydrophilic substituents, as described byformula (II) (DS_(II)) and/or the level of polyalkoxylation within ahydrophilic substituent can be provided such that the galactomannanretains or attains a desired amount of water solubility. In other words,various levels of DS_(I) and DS_(II) can vary according to the desiredbalance between cationic efficacy and solubility characteristics. Thetotal degree of substitution, defined as (DS), is the sum of the degreeof substitution of substituents defined by formula (I) (DS_(I)) and thedegree of substitution of substituents defined by formula (II)(DS_(II)).

In one embodiment, the level of the substituents defined under formula(I) or DS_(I) ranges from about 0 to about 2.9999, from about 0 to about2.499 in another aspect, from about 0 to about 1.99 in still anotheraspect, from about 0 to about 0.99 in a further aspect, from about 0 toabout 0.8 in a still further aspect, and from about 0 to about 0.7 in anadditional aspect of the invention. The level of the substituentsdefined under formula (II) or DS_(II) ranges from about 0.0001 to about3 in one aspect, from about 0.001 to about 2.5 in another aspect, fromabout 0.01 to about 2 in still another aspect, from about 0.01 to about1 in a further aspect, from about 0.01 to about 0.5 in still a furtheraspect, and from about 0.01 to about 0.3 in an additional aspect of theinvention. The total average DS or DS_(total) for combined substituentsof formulas (I) and (II) can range from 0.0001 to about 3 or above inone aspect, from 0.1 to about 2.5 in another aspect, from 0.2 to 2 in afurther aspect, and from about 0.3 to about 1 in a still further aspectof the invention per constituent glycoside residual unit in thegalactomannan backbone. As previously described, when R² in formula (II)is a cationic moiety represented by AR, the cationic moiety in formula(I) is optionally present. Accordingly, when AR in formula (I) is notpresent the DS_(I) is 0. As the skilled artisan will recognize thedegree of substitution for both DS_(I) and DS_(II) will fall within thestated ranges for DS_(total).

The degree of cationic substitution (DS_(cat)) on the Cassiagalactomannan polymer can be represented by the sum of DS_(I) and thedegree of substitution of a hydrophilic moiety containing a cationicsubstituent as represented by formula (II) where R² is AR(DS_(II with cat)). The degree of hydrophilic substitution(DS_(hydrophile)) on the Cassia galactomannan is equivalent to DS_(II),which in one aspect contains both hydrophilic moieties and cationicmoieties (DS_(II with cat)), and in another aspect DS_(II) solelycontains hydrophilic moieties (DS_(II without cat)). The degree ofcationic and hydrophilic substitution on the Cassia galactomannan can beschematically represented by the following equations:

DS _(cat) =DS _(I) +DS _(II with cat)

DS _(hydrophile) =DS _(II with cat) +DS _(II without cat)

wherein DS_(cat), DS_(hydrophile), DS_(I), DS_(II with cat), andDS_(II without cat) are as defined above.

In one aspect, DS_(cat) ranges from about 0.0001 to about 3, from about0.001 to about 2.5 in another aspect, from about 0.01 to about 2 instill another aspect, from about 0.1 to about 1 in a further aspect,from about 0.2 to about 0.8 in a still further aspect, and from about0.3 to about 0.7 in an additional aspect of the invention. In oneaspect, DS_(hydrophile) ranges from about 0.0001 to about 3, from about0.001 to about 2.5 in another aspect, from about 0.01 to about 2 instill another aspect, from about 0.01 to about 1 in a further aspect,and from about 0.01 to about 0.3 in a still further aspect of theinvention.

In one embodiment of the invention, a portion of or all of the hydrogenatoms situated on the hydroxyl groups present on the Cassiagalactomannan are substituted with a substituent selected from one ormore cationic substituents independently represented by formula (I) andone or more hydrophilic substituents independently represented byformula (II), wherein R² is independently selected from hydrogen andmethyl. For illustrative purposes, and without limitation thereto, thisembodiment can be schematically represented by formula (IV) as follows:

wherein the bracketed moiety, independently, represents a glycosideresidual unit of the Cassia galactomannan, and AR, A, R¹, a, b, and care as previously defined and R², independently, is selected fromhydrogen and methyl.

In another embodiment of the invention, a portion of or all of thehydrogen atoms situated on the hydroxyl groups present on the Cassiagalactomannan are substituted with a substituent selected from one ormore cationic substituents independently represented by formula (I), oneor more hydrophilic substituents independently represented by formula(II), wherein R² is independently selected from hydrogen and methyl, andone or more hydrophilic substituents represented by formula (II),wherein R^(2′) is independently selected from AR. For illustrativepurposes, and without limitation thereto, this embodiment can beschematically represented by formula (V) as follows:

wherein the bracketed moiety, independently, represents a glycosideresidual unit of the Cassia galactomannan, and AR, A, R¹, a, b, and care as previously defined, R², independently, is selected from hydrogenand methyl, and R^(2′), independently, is selected from hydrogen,methyl, and AR.

In further embodiment of the invention, a portion of or all of thehydrogen atoms situated on the hydroxyl groups present on the Cassiagalactomannan are substituted with a substituent selected from one ormore cationic substituents independently represented by formula (I) andone or more substituents independently represented by formula (II)containing both a hydrophilic moiety and a cationic moiety. Forillustrative purposes, and without limitation thereto, this embodimentcan be schematically represented by formula (VI) as follows:

wherein the bracketed moiety, independently, represents a glycosideresidual unit of a Cassia galactomannan, and AR, A, R¹, a, b, and c areas previously defined.

In another embodiment of the invention, a portion of or all of thehydrogen atoms situated on the hydroxyl groups present on the Cassiagalactomannan are substituted with a substituent selected from one ormore hydrophilic substituents independently represented by formula (II)containing both a hydrophilic moiety and a cationic moiety. Forillustrative purposes, and without limitation thereto, this embodimentcan be schematically represented by formula (VII) as follows:

wherein the bracketed moiety, independently, represents glycosideresidual unit of a Cassia galactomannan, and AR, A, R¹, a, b, and c areas previously defined. In this embodiment the hydrophilic moiety isterminated with a cationic substitutent.

In a still further embodiment of the invention, a portion of or all ofthe hydrogen atoms situated on the hydroxyl groups present on the Cassiagalactomannan are substituted with a substituent selected from one ormore hydrophilic substituents independently represented by formula (II),wherein R², independently, is selected from hydrogen and methyl and oneor more hydrophilic substituents independently represented by formula(II), wherein R^(2′) is independently selected from AR. When R^(2′) isAR, the substituent represented by formula (II) contains both ahydrophilic moiety and a cationic moiety. For illustrative purposes, andwithout limitation thereto, this embodiment can be schematicallyrepresented by formula (VIII) as follows:

wherein the bracketed moiety, independently, represents a glycosideresidual unit of a Cassia galactomannan, and AR, A, R¹, a, b, and c areas previously defined, R², independently, is selected from hydrogen andmethyl, and R^(2′), independently, represents AR.

The embodiments schematically depicted in formulae (IV), (V), (VI),(VII), and (VIII) above are disclosed for illustrative purposes and arenot to be construed as a limitation upon the scope of the invention.While only glycoside residual units having an average of 3 hydroxylsubstitution sites are illustrated, as discussed previously, thegalactomannan backbone also contains recurring galactosyl side unitshaving a potential DS of about 4 (3 hydroxyl units are bonded directlyto the galactosyl ring and a fourth hydroxyl unit is attached to the C-6carbon atom). Although the foregoing schematic formulae depict high DSvalues (e.g., 2 or 3 per repeating unit), it should be recognized thatthis is for illustrative purposes only, and as discussed above theactual DS value is an average (per glycoside unit) that represents allof the hydroxyl groups contained on the galactomannan backbone aspotential substitution sites. Further, it is pointed out in the aboveschematic formulae that the methylene group attached to the C-6 carbonatom as well as the glycosidic linkage between repeating units in thegalactomannan backbone is not shown.

The hydrophilic derivation (hydrophilization) can be conducted byutilizing a hydrophilization agent such as an alkoxylating agent and thecationic derivation (cationization) can be accomplished through theutilization of a cationization agent such as a quaternizing agent.Furthermore, one or more hydrophilization or cationization agents can becombined to reduce the number of synthesis steps or to achieve differentbalances of various hydrophilic and cationic substituents on the Cassiagalactomannan backbone. Cationically and hydrophilically modified Cassiagalactomannans of this invention can be prepared (1) by hydrophilizationfollowed by cationization; (2) cationization followed byhydrophilization; (3) simultaneous hydrophilization and cationization;(4) a sequential series of hydrophilization steps followed by asequential series of cationization steps; (5) a sequential series ofcationization steps followed by a sequential series of hydrophilizationsteps; (6) alternating hydrophilization and cationization steps; and (7)or any variation of the foregoing procedures.

In one embodiment of the invention, hydrophilization involves reactingthe pendant hydroxyl groups present on the backbone of the cassiagalactomannan or derivative thereof with an alkoxylation agent. In oneaspect, the alkoxylation agent can be selected from alkylene oxide suchas ethylene oxide, propylene oxide, butylene oxide (1,2 epoxy butane or2,3 epoxy butane), and mixtures thereof. In this embodiment, the Cassiagalactomannan is dissolved, dispersed, or slurried in a suitable solventand in the presence of an acidic or basic catalyst. Catalysts suitablefor this reaction are well-known in the art and include, for example,inorganic alkalis such as alkali metal oxides and hydroxides, e.g.,sodium hydroxide, potassium hydroxide, calcium hydroxide, sodiummethoxide, sodium borohydride; protic and Lewis acids, e.g., borontrifluoride, stannic chloride and sulfuric acid. Amines, quaternaryammonium compounds, other acids known in the art for this type ofreaction can also be employed. Mixtures of catalysts may also beemployed. In one aspect, a basic catalyst can be used in thepolyalkoxylation reaction employing from about 0.1 to about 10 weightpercent of potassium or sodium hydroxide, sodium methoxide, sodiumborohydride or mixtures thereof, based on the weight of thegalactomannan. The reaction can be carried out at a temperature rangingfrom about 40° C. to about 200° C., although higher or lowertemperatures may be utilized. The reaction can be run at substantiallyatmospheric pressure, although the reaction can be carried out in anautoclave at pressures of from about 10 psig to about 80 psig. Theamount of alkylene oxide (e.g., ethylene oxide and/or propylene oxide)introduced to the reaction zone, and the duration of the reaction time,determines the number of moles alkylene oxide repeating units added tothe hydroxyl moiety(ies) on the galactomannan backbone. As noted above,the polyalkoxylated substituents can be prepared by reacting mixtures ofethylene oxide and propylene oxide, resulting in hydrophilicallymodified Cassia galactomannans containing random and/or blockarrangements of alkylene oxide units. It is typical of propylene oxideto yield isopropylene oxide repeating units upon opening of the epoxidering during the polyalkoxylation reaction.

In another aspect, the hydrophilization reagent is a preformedpolyalkoxylated compound that contains a functional group that isco-reactive with a hydroxyl group on the cassia galactomannan backbone.In one aspect of the invention, the functional group can be selectedfrom a halohydrin and/or an epoxy group that is reactive with a pendanthydroxyl group on the galactomannan backbone. A suitable preformedpolyalkoxylated compound can be represented by formula (IX) below:

wherein A′ is an epoxylated linear and branched C₃-C₆ alkyl group whichcan be optionally substituted with one or more halogen groups (e.g.chloro, bromo) or a halogenated (e.g., chloro, bromo) linear andbranched C₃-C₆ alkyl group which can be substituted with one or morehydroxyl groups, and R¹, R², and c are as previously defined. In anotheraspect, the hydrophilization reagent can be represented by formulae (X)and (XI) below:

wherein X represents a halogen selected from chlorine and bromine; m isan integer from 1 to 4; and n is an integer from 1 to 5. In one aspect,A′ represents epoxyalkyl radical and in another aspect A′ represents a3-halogeno-2-hydroxypropyl radical.

Representative epoxylated alkyl radicals set forth under formula (X)include but are not limited to 2,3-epoxypropyl, 3,4-epoxybutyl,4,5-epoxypentyl, and 5,6-epoxyhexyl groups. Representative halogenatedlinear and branched alkyl radicals set forth under formula (XI) includebut are not limited to 2-chloroethyl, 2-bromoethyl, 3-chloropropyl,4-chlorobutyl, 6-chlorohexyl, and 2-hydroxy-3-chloropropyl groups.

The degree of alkoxylation (as defined by c in formula II) contained inthe hydrophilic substituent group reacted onto the cassia galactomannancan be varied from about 1 to about 250 repeat units in one aspect, fromabout 2 to about 200 repeat units in another aspect, from about 2 toabout 150 repeat units in still another aspect, from about 5 to about100 repeat units in a further aspect, and from about 10 to about 50repeat units in a still further aspect of the invention. The alkyleneoxide unit(s) in the polyoxyalkylene moiety is selected from ethyleneoxide, isopropylene oxide, butylene oxide, and combinations thereof. Thealkylene oxide units can be arranged as a homopolymer, a randomcopolymer, and a block copolymer.

The hydrophilization reaction of the Cassia galactomannan or derivativethereof according to this aspect is conducted by dissolving, dispersing,or slurrying the galactomannan in a suitable (inert) solvent or diluentand reacting it with a preformed polyalkoxylating reagent represented byformula (IX) as defined above. The polyalkoxylating reagent can be usedeither singly as a combination of two or more. The reaction can beconducted in solvent and in the presence of a catalyst such as thosedescribed above for the alkylene oxide hydrophilization reagents. In oneaspect, alkali metal hydroxides, e.g., sodium hydroxide, potassiumhydroxide, calcium hydroxide, are suitable for use as catalysts. Thealkali metal hydroxide catalysts are used in conventional amounts knownin the art and are generally employed in an amount ranging from about0.1 weight percent to about 50 weight percent based on the weight of thegalactomannan to be modified, depending on the alkoxide used. Thereaction temperature can range from about 0 to about 150° C. in oneaspect, 30 to 100° C. in another aspect, and 40 to 80° C. in a furtheraspect of the invention

Examples of suitable solvents or diluents for the hydrophilizationreactions involving the alkylene oxide or the preformed polyalkoxylatedcompound described above include but are not limited to lower aliphaticalcohols, such as ethanol, propanol, isopropanol, tert-butyl alcohol;ketones, such as acetone and methyl ethyl ketone; or liquidhydrocarbons; such as hexane, cyclohexane, xylene, toluene and mixturesthereof. Mixtures of the foregoing solvents or diluents with water canalso be used so long as the water does not interfere with the reaction.In one aspect of the invention, an aqueous isopropanol diluent havingwater to isopropanol ratio ranging from 5 wt % water:95 wt % IPA to 80wt % water:20 wt % IPA is utilized in the reaction.

Cationization of the galactomannan can be effected by reacting thependant hydroxyl groups present on the backbone of the Cassiagalactomannan and/or hydroxyl groups present on a hydrophilicallymodified derivative thereof with a cationization agent. Thecationization agent contains a functional group that is reactive withthe hydroxyl groups on a cassia galactomannan glycoside and/or ahydroxyl terminated hydrophilic group that has previously been appendedto the galactomannan backbone. In one aspect of the invention, thehydroxyl reactive functional group can be selected from a halohydrinand/or an epoxy group that is reactive with a pendant hydroxyl group onthe galactomannan backbone and/or a hydroxyl terminated hydrophilicgroup. A suitable cationization agent can be represented by formulae(XII) and (XIII) below:

wherein A′ is as defined above and represents an epoxylated linear andbranched C₃-C₆ alkyl group which can be optionally substituted with oneor more halogen groups (e.g., chloro, bromo) or a halogenated (e.g.,chloro, bromo) linear and branched C₃-C₆ alkyl group which can besubstituted with one or more hydroxyl groups; A is a linear and branchedC₃-C₆ alkylene group which can be optionally substituted with one ormore halogen groups (e.g., chloro, bromo) or hydroxyl groups. In oneaspect, A′ represents glycidyl radical and in another aspect A′represents a 3-halogeno-2-hydroxypropyl radical. The R substituent,independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and —P⁺R³R⁴R⁵X⁻,wherein R³ and R⁴, and R⁵, independently, are selected from hydrogen andlinear and branched C₁-C₂₄ alkyl; and X⁻ represents an anion selectedfrom chloride, bromide, iodide, sulfate, methylsulfate, sulfonate,nitrate, phosphate, and acetate. The (R¹—O)_(c) moiety represents apolyoxyalkylene group wherein the individual repeating units arearranged as a homopolymer, a random copolymer or a block copolymer ofoxyalkylene units, wherein R¹, independently, is selected from linearand branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups, and c is aninteger ranging from about 1 to about 250. In another aspect, R is aquaternium nitrogen radical represented by the formula —N⁺R³R⁴R⁵X⁻,wherein R³, R⁴, and R⁵, independently, are selected from hydrogen andlinear and branched C₁-C₂₄ alkyl groups, and X⁻ represents an anionselected from chloride, bromide, iodide, sulfate, methylsulfate,sulfonate, nitrate, phosphate, and acetate. Representative alkyl groupsdefined under R³, R⁴, and R⁵ include but are not limited to methyl,ethyl, propyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl,dococyl, and combinations thereof. Representative oxyalkylene unitsinclude but are not limited to ethoxy, propoxy, isopropoxy, and butoxy,and combinations thereof. In another aspect, R³ is selected from C₁-C₈alkyl, and R⁴ and R⁵, independently, are selected from C₈-C₂₄ alkyl. Ina further aspect, R³ and R⁴, independently, are selected from C₁-C₈alkyl and R⁵ is selected from C₈-C₂₄ alkyl. In a still furtherembodiment, R³, R⁴ and R⁵ are, independently selected, from C₁-C₁₀ alkylin one aspect, from C₁-C₈ alkyl in another aspect, and from C₁-C₅ alkylin a further aspect. In another embodiment, R³, R⁴ and R⁵ are eachmethyl. In all of the foregoing aspects, X⁻ is as previously defined. Ina further aspect, A′ can be represented by formulae (X) and (XI) aspreviously defined.

The introduction of the cation containing moiety onto thepolygalactomannan backbone via a functionalization reagent conforming toformulae (XII) and (XIII) and/or can be conducted by known techniques.For example, the reaction between the hydroxyl groups appended on or tothe polygalactomannan backbone with various quaternizing reagents suchas 3-chloro-2-hydroxypropyltrialkylammonium salts and2,3-epoxypropyltrialkyl ammonium salts can be conducted under the sameconditions as set forth above for the hydrophilization reagents definedunder formula (IX). In one embodiment, suitable cationizing reagentsinclude but are not limited to glycidyltrimethylammonium chloride,glycidyltriethylammonium chloride, glycidyltripropylammonium chloride,glycidylethyldimethylammonium chloride, glycidyidiethylmethylammoniumchloride, and their corresponding bromides and iodides;3-chloro-2-hydroxypropyltrimethylammonium chloride,3-chloro-2-hydroxypropyltriethylammonium chloride,3-chloro-2-hydroxypropyltripropylammonium chloride,3-chloro-2-hydroxypropylethyldimethylammonium chloride, and theircorresponding bromides and iodides. In another embodiment, thecationization reaction can be conducted with a hydroxyl group providedby the hydrophilic moiety, e.g., subsequent to hydrophilization viaalkoxylation with alkylene oxide(s) or a preformed hydroxyl terminatedpolyalkoxylated compound.

In the preparation of the cationically and hydrophilically modifiedpolygalactomannans of the present invention, a hydroxyl group(s) on thepolygalactomannan backbone is reacted with a functionalizationreagent(s) set forth, for example, under formulae (IX), (X), (XI),(XII), and (XIII) described above, such that a hydrogen atom situated onsaid hydroxyl group(s) is replaced by a substituent or residue definedunder formulae (I) and (II) above, subject to the proviso that thederivatized galactomannan backbone contains at least one hydrophilicmoiety comprising a alkylene oxide and/or polyoxyalkylene group and atleast one moiety comprising a cationic group. When the hydrophilicmoiety contains a cationic group, e.g., wherein R² is AR, the AR moietydescribed under formula (I) is optionally present The reaction can beschematically represented as follows:

wherein D is selected from hydrogen, a residue or moiety obtained from afunctionalization reagent(s) described above, and combinations thereof.In another aspect of the invention, D represents hydrogen, a moietyselected from formulae (I), a moiety selected from formula (II), andcombinations thereof subject to the provisos set forth above.

In synthesizing the cationically and hydrophilically modified Cassiapolygalactomannan polymers of this invention, the functionalizingreagent will be capable of reacting with hydroxyl groups present in thegalactosyl side unit and/or the mannosyl main chain backbone units ofthe Cassia polymer. For instance, the functionalizing reagent will becapable of reacting with hydroxyl groups on the C-2, C-3, C-4, and/orC-6 carbon atoms of the galactosyl side unit and/or the C-2, C-3, or C-6carbon atoms of the mannosyl main chain units of the polymer. Thecationically and hydrophilically modified Cassia galactomannan of thisinvention can be produced from readily available materials. Suchcompositions are derived from naturally occurring Cassia endospermsplits as discussed above, or can be derived from commercially availablecationically derivatized cassia such as disclosed in U.S. Pat. No.4,753,659 and U.S. Pat. No. 7,262,157, which are herein incorporated byreference for their disclosure of cationically derivatized Cassia.

According to an embodiment of the invention, the cationic andhydrophilic modification can be carried out starting from unmodifiedCassia galactomannan as such or from a partially substituted Cassiagalactomannan (e.g., partially substituted with cationic and/orhydrophilic substituents). The cationic and hydrophilic derivatizationsteps can be conducted in any order, or simultaneously, as well asrepeated, to produce the desired cationically and hydrophilicallymodified Cassia galactomannan of the invention. The hydrophilic andcationic modification of the Cassia galactomannan can be carried outwithout isolating the intermediate product.

Underivatized Cassia gum or flour is commercially available fromLubrizol Advanced Materials, Inc. under the Diagum trademark. Thederivatization of hydroxyl groups on Cassia polygalactomannan can beaccomplished by methods well known to those skilled in the art.Generally speaking, the hydroxyl groups of the Cassia can be reactedwith any functionalization reagent that is co-reactive therewith. Forexample, to functionalize the hydroxyl group of the Cassia with acationic substituent of this invention, the hydroxyl group(s) on theCassia gum polygalactomannan are reacted with a functionalizationreagent that contains a cationic group and a functional moiety that isco-reactive with the hydroxyl groups, such as an epoxy group and ahaloalkyl group. The functionalization reaction is conducted in anappropriate solvent and at an appropriate temperature. The amount offunctional group substitution (degree of substitution) on thepolygalactomannan hydroxyl atom(s) can be controlled by adjusting thestoichiometric amount of functionalization reagent added to the Cassiapolygalactomannan. Functionalization methods for Cassia gumpolygalactomannans are disclosed in U.S. Pat. No. 4,753,659. Additionalmethods of derivatizing polygalactomannans are set forth in U.S. Pat.No. 5,733,854. The teachings of U.S. Pat. No. 4,753,659 and U.S. Pat.No. 5,733,854 are incorporated herein by reference for the purpose ofillustrating methods for functionalizing Cassia gum polygalactomannans.

The Cassia used as a starting material is typically in powder form andis normally treated with an alcohol or an alcohol/water solution. Inpractice, the alcohol used can be methanol, ethanol, isopropanol,n-propyl alcohol, n-butyl alcohol, isobutyl-alcohol, t-butyl alcohol, orthe like. The alcohol can be used in neat (100%) form or as a aqueoussolution. In such cases it is, of course, critical for the alcohol to bemiscible with water. This treatment step is typically done at ambienttemperatures (about 20° C.). However, it can optionally be done at anytemperature which is within the range of about 0° C. to about 70° C. Insome cases, it is advantageous to conduct this treatment step at anelevated temperature, which is within the range of about 30° C. up toabout 70° C.

In practice, it is generally preferred to use mixtures of water andorganic solvents in the Cassia treatment step. Particularly effectiveresults occur when using between about 10 to about 90 percent water byweight and between about 90 to about 10 percent organic solvent byweight. Most preferred is the use of between about 30 to about 80% byweight isopropyl alcohol and between about 20 to about 70% by weightwater. For example, excellent results have been obtained wherein thesolution selected for use is an isopropanol/water mixture, wherein therespective amounts by weight are 44% isopropanol and 54% water. Theamount of alcohol or alcohol water solution to be used in this step isthat amount which is necessary to fully saturate the Cassia powder. Inpractice, this amount is usually at least about twice the amount byweight of the starting Cassia powder, and even more preferably, at leastabout three times the amount by weight of the starting Cassia.

After addition of the alcohol or alcohol/water solution and thesubsequent neutralization, followed by agitation as needed, thefunctionalizing agent is added to the Cassia solution. As previouslyexplained, the functionalizing agent is a compound that contains atleast one functional group that is capable of reacting with hydroxylgroups on the Cassia. These functional groups can be epoxy groups,halogen containing groups. The amount of functionalizing reagent addedto the Cassia solution is the amount that yields a desired total degreeof substitution. The degree of substitution will typically be within therange of 0.0001 to 3 and will more typically be within the range of 0.1to 2.5. In many cases, the degree of substitution will be within therange of 0.2 to 2. For purposes of this invention, the degree ofsubstitution is equal to the number of moles of functionalization permole of galactose and mannose repeat units in the Cassia polymer.

To facilitate the reaction kinetics of the functionalization reaction,an alkaline material can be added as a catalyst. The alkaline materialis typically an aqueous solution of a base, such as sodium hydroxide(NaOH). The aqueous solution will preferably contain at least 12% NaOH,and more preferably 12% to 60% NaOH. Even more preferred is treatmentwith a 20% to a 50% aqueous NaOH solution. In the preferred embodiment,between about 0.1 and about 50 parts of NaOH (100%) are added for every100 parts of Cassia starting material.

The temperature of the reaction mixture can be increased to betweenabout 40° C. to about 75° C., with a reaction temperature in the rangeof about 60° C. to about 70° C. being even more preferred. The mixtureis typically stirred for a period of time sufficient to insure completereaction of the reactants. In practice, this reaction time is generallybetween about 1 hour to about 5 hours, with a reaction time within therange of about 2 hours to about 4 hours being more preferred.

After being functionalized, the Cassia is neutralized. Theneutralization is normally done to a pH which is within the range ofabout 6 to about 8 (preferably about 7). Any acid may be selected foruse to neutralize the solution, including strong acids such ashydrochloric acid and sulfuric acid or weak acids such as acetic acid,citric acid, carbone dioxide (carbonic acid), trifluoroacetic acid, etc.In a preferred embodiment, either hydrochloric or acetic acid is used.The amount of acid used is the amount necessarily for neutralization.

After the neutralization, the functionalized Cassia is typicallyfiltered and then washed with water, an organic solvent, or a mixture ofboth. When utilizing organic solvent water mixtures the organicsolvent(s) are water miscible solvents including alcohols, such asmethanol, ethanol, isopropanol, n-propyl alcohol, n-butyl alcohol,iso-butyl alcohol, t-butyl alcohol, and the like. Other commonly usedpurification solvents such as acetone, glycols and the like mayalternatively be selected. Mixtures of these solvents with the abovedisclosed water miscible alcohols are also useful.

The volume of the wash liquid is much greater than the amount of treatedCassia and can be performed in batch wise or multiple applications. Inpreferred practices, the volume of the wash liquid is at least twice thevolume of the functionalized Cassia and is preferably at least threetimes the volume of the Cassia. It is preferable to conduct 1 to 4independent wash cycles. However, more than 4 wash cycles can be used ifneeded. The concentration of the wash liquid for each cycle can be thesame or different. For example, washing of the Cassia powder may beaccomplished by first washing with a dilute isopropyl alcohol solution,followed by washing with stronger solutions of isopropyl alcohol, andfinally with acetone. After washing, the functionalized Cassia can bedried and recovered using methods known in the art. Examples of suchtechniques include air drying, filtering, evaporative drying,centrifuging, flash grinding, addition of solvents, freeze drying, andthe like. The use of fluidized bed drying can be advantageous.

In one aspect of the invention, the hydrophilic functionalization ofunderivatized Cassia can be accomplished by reacting an epoxy groupcontaining hydrophilic functionalizing reagent with a hydroxyl group(s)on the backbone units of the Cassia galactomannan. The reaction can beschematically depicted as follows:

wherein R¹, independently, represents a divalent C₁-C₄ alkylene radical;R², independently, represents hydrogen and methyl; n represents thenumber of hydroxyl groups on the cassia galactomannan backbone; c is aspreviously defined; x represents the average total substitution of thehydrophilic moiety on the galactomannan backbone, wherein x can not begreater than n; and the result of the difference of n−x represents thefree hydroxyl groups remaining on the derivatized backbone.

In another aspect, the hydrophilic functionalization of underivatizedCassia can be accomplished by reacting a (C₁-C₄) alkylene oxidefunctionalizing reagent with a hydroxyl group(s) on the backbone unitsof the Cassia galactomannan. This reaction can be schematically depictedas follows:

wherein R¹, independently, represents a divalent C₁-C₄ alkylene radical;n represents the number of hydroxyl groups on the cassia galactomannanbackbone; c is as previously defined; x represents the average totalsubstitution of the hydrophilic moiety on the galactomannan backbone,wherein x can not be greater than n; and the result of the difference ofn−x represents the free hydroxyl groups remaining on the derivatizedCassia backbone.

The hydrophilically modified cassia galactomannan product obtained inthe reactions schematically represented by (XIV) and (XV) above can becationically derivatized to obtain the cationically and hydrophilicallymodified cassia galactomannans of the invention. In one embodiment, thereaction product obtained in reaction scheme (XIV) is reacted with acationic functionalization reagent as follows:

wherein R¹, independently, represents a divalent C₁-C₄ alkylene radical;R², independently, represents hydrogen and methyl; R², independently, isselected from hydrogen, methyl and

R³, R⁴, and R⁵, independently, are selected from hydrogen and linear andbranched C₁-C₂₄ alkyl groups; X⁻ represents an anion selected fromchloride, bromide, iodide, sulfate, methylsulfate, sulfonate, nitrate,phosphate, and acetate; n represents the number of hydroxyl groups onthe cassia galactomannan backbone; c is as previously defined; xrepresents the average total substitution of the hydrophilic moiety onthe galactomannan backbone; y represents the average total cationicsubstitution on the hydrophilically derivatized cassia galactomannanbackbone, wherein the sum of x and y can not be greater than n; and theresult of the difference of n−x represents the free hydroxyl groupsremaining on the derivatized backbone.

In another embodiment, the reaction product obtained in reaction scheme(XV) is reacted with a cationic functionalization reagent as follows:

wherein R¹, independently, represents a divalent C₁-C₄ alkylene radical;R^(2′), independently, is selected from hydrogen, and

where R³, R⁴, and R⁵, independently, are selected from hydrogen andlinear and branched C₁-C₂₄ alkyl groups; X⁻ represents an anion selectedfrom chloride, bromide, iodide, sulfate, methylsulfate, sulfonate,nitrate, phosphate, and acetate; n represents the number of hydroxylgroups on the cassia galactomannan backbone; c is as previously defined;x represents the average total degree of substitution of the hydrophilicmoiety on the galactomannan backbone; y represents the average totaldegree of cationic substitution on the hydrophilically derivatizedcassia galactomannan backbone, wherein the sum of x and y can not begreater than n; and the result of the difference of n−x represents thefree hydroxyl groups remaining on the derivatized backbone.

In one aspect of the invention set forth in reaction schemes (XIV) and(XV) depicted above, underivatized Cassia is subjected to ahydrophilization reaction to obtain a hydrophilically modifiedproduct(s). The hydrophilically modified product(s) is subsequentlyderivatized with a cationic functionalization reagent as set forth inreaction schemes (XVI) and (XVII) to obtain the cationically andhydrophilically modified Cassia galactomannan of the invention. Asdiscussed above, it is readily apparent to the artisan of ordinary skillin the art that the cationically and hydrophilically modified Cassiagalactomannans of the invention can also be prepared by reacting anepoxy group containing cationic functionalizing reagent selected fromformulae (XII), (XIII) and mixtures thereof with a hydroxyl group(s) onthe backbone units of underivatized Cassia galactomannan followed bysubsequent hydrophilization with a hydrophilization reagent selectedfrom a (C₁-C₄) alkylene oxide or a hydrophilization reagent conformingto formula (IX). As set forth previously, any of the following reactionschemes can be utilized to synthesize the hydrophilically modified,cationic Cassia galactomannans of the invention (1) hydrophilizationfollowed by cationization; (2) cationization followed byhydrophilization; (3) simultaneous hydrophilization and cationization;(4) a sequential series of hydrophilization steps followed by asequential series of cationization steps; (5) a sequential series ofcationization steps followed by a sequential series of hydrophilizationsteps; (6) alternating hydrophilization and cationization steps; and (7)any variation of the foregoing procedures.

The hydrophilically modified, cationic derivatized Cassia galactomannansof this invention can be employed as deposition aids, film formers,conditioners, fixative agents, emulsifiers, stabilizers, moisturizers,spreading aids and carriers for enhancing the efficacy, deposition ordelivery of chemically and physiologically active ingredients andcosmetic materials, and as vehicles for improving the psychosensory, andaesthetic properties of a formulation in which they are included. Thecationic character of the cationically and hydrophilically modifiedCassia polymers of this invention makes them useful as antistaticagents, and, under certain conditions, may also provide biocidal,bacteriostatic, preservative, and anti-microbial activity. These polymercompositions can be utilized in a variety of products for personal care,health care, household care, institutional and industrial (collectively“I&I”) care, and in a variety of products for medical and industrialapplications. The cationically and hydrophilically modified Cassiapolymer compositions of this invention are preferably incorporated incompositions that are non-alkaline, i.e., acidic to substantiallyneutral in pH, but are not limited thereto.

Some embodiments of the invention relate to the use of cationically andhydrophilically modified Cassia derivatives as multi-functional polymeringredients in personal care, health care, household, institutional andindustrial product applications and the like. The cationically andhydrophilically modified Cassia polymers can be employed as emulsifiers,spreading aids and carriers for enhancing the efficacy, deposition anddelivery of chemically and physiologically active ingredients andcosmetic materials, and as a vehicle for improving the psychosensory andaesthetic properties of a formulation in which they are included. Theterm “personal care products” as used herein includes, withoutlimitation, cosmetics, toiletries, cosmeceuticals, beauty aids, personalhygiene and cleansing products that are applied to the skin, hair,scalp, and nails of humans and animals. The term “health care products”as used herein includes, without limitation, pharmaceuticals,pharmacosmetics, oral care products (mouth, teeth), eye care products,ear care products and over-the-counter products and appliances, such aspatches, plasters, dressings and the like. The term also includesmedical devices that are externally applied to or into the body ofhumans and animals for ameliorating a health related or medicalcondition. The term “body” includes the keratinous (hair, nails) andnon-keratinous skin areas of the entire body (face, trunk, limbs, handsand feet), the tissues of body openings and the eyes. The term “skin”includes the scalp and mucous membranes. The term “household careproducts” as used herein includes, without limitation, products beingemployed in a household for surface protection and/or cleaning includingbiocidal cleaning products for maintaining sanitary conditions in thekitchen and bathroom and laundry products for fabric cleaning and thelike. The term “institutional and industrial products” as used hereinincludes, without limitation, products employed for protection and/orcleaning or maintaining sanitary conditions in industrial andinstitutional environments, including hospitals and health carefacilities, and the like.

The amount of cationically and hydrophilically modified polymer that canbe employed depends upon the purpose for which it is included in theformulation and can be readily determined by person skilled in theformulation arts. Thus, as long as the physicochemical and functionalproperties of the compositions containing the cationically andhydrophilically modified polymer composition are achieved, a usefulamount of the polymer, active weight percent, on a total compositionweight basis, typically can vary in the range of about 0.01% to about50%, but is not limited thereto. In a given composition or application,therefore, the cationically and hydrophilically modified polymercomposition of this invention can, but need not, serve more than onefunction, such as thickener and conditioner, film-former and carrier,and the like, as described in more detail below.

Compositions containing the cationically and hydrophilically modifiedCassia polymer composition of this invention can be packaged anddispensed from containers, such as jars, bottles, tubes, spray bottles,wipes, cans, roll-on containers, stick containers, and the like, withoutlimitation. There is no limitation as to the form of product in whichthe cationically and hydrophilically modified polymer composition can beincorporated, so long as the purpose for which the product is used isachieved. For example, personal care and health care products containingthe cationically and hydrophilically modified polymer composition can beapplied to the skin, hair, scalp and nails in the form of, without beinglimited thereto, gels, sprays (liquid or foam), emulsions (creams,lotions, pastes), liquids (rinses, shampoos), bars, ointments,suppositories, impregnated wipes, patches, and the like.

The cationically and hydrophilically modified polymer compositions ofthe invention are suitable for the preparation of personal care(cosmetics, toiletries, cosmeceuticals) and topical health careproducts, including without limitation, hair care products, such asshampoos (including combination shampoos, such as “two-in-one”conditioning shampoos); post-shampoo rinses; setting and stylemaintenance agents including setting aids, such as gels and sprays,grooming aids, such as pomades, conditioners, perms, relaxers, hairsmoothing products, and the like; skin care products (facial, body,hands, scalp and feet), such as creams, lotions, conditioners, andcleansing products; antiacne products; antiaging products (exfoliant,keratolytic, anticellulite, antiwrinkle, and the like); skin protectantssuch as sunscreens, sunblock, barrier creams, oils, silicones, and thelike; skin color products (whiteners, lighteners, sunless tanningaccelerators, and the like); hair colorants (hair dyes, hair colorrinses, highlighters, bleaches and the like); pigmented skin colorants(face and body makeups, foundation creams, mascara, rouge, lip products,and the like); bath and shower products (body cleansers, body wash,shower gel, liquid soap, soap bars, syndet bars, conditioning liquidbath oil, bubble bath, bath powders, and the like); nail care products(polishes, polish removers, strengtheners, lengtheners, hardeners,cuticle removers, softeners, and the like); and any aqueous acidic tosubstantially neutral to basic composition to which an effective amountof the present polymers can be incorporated for achieving a beneficialor desirable, physical or chemical, effect therein during storage and/orusage.

Toiletries and health and beauty aids, commonly referred to as HBAs,containing the cationically and hydrophilically modified polymercomposition of this invention, can include, without limitation,hair-removal products (shaving creams and lotions, depilatories,after-shave skin conditioners, and the like); deodorants andantiperspirants; oral care products (mouth, teeth and gums), such asmouthwash, dentifrice, such as toothpaste, tooth powder, tooth polishes,tooth whiteners, breath fresheners, denture adhesives, and the like;facial and body hair bleach; and the like. Other health and beauty aidsthat can contain the present cationically and hydrophilically modifiedpolymers, include, without limitation, sunless tanning applicationscontaining artificial tanning accelerators, such as dihydroxyacetone(DHA), tyrosine, tyrosine esters, and the like; skin depigmenting,whitening, and lightening formulations containing such activeingredients as kojic acid, hydroquinone, arbutin, fruital, vegetal orplant extracts, (lemon peel extract, chamomile, green tea, papermulberry extract, and the like), ascorbyl acid derivatives (ascorbylpalmitate, ascorbyl stearate, magnesium ascorbyl phosphate, and thelike); foot care products, such as keratolytic corn and callousremovers, foot soaks, foot powders (medicated, such as antifungalathlete's foot powder, ointments, sprays, and the like, andantiperspirant powders, or non-medicated moisture absorbent powder),liquid foot sprays (non-medicated, such as cooling, and deodorantsprays, and medicated antifungal sprays, antiperspirant sprays, and thelike), and foot and toenail conditioners (lotions and creams, nailsofteners, and the like).

Topical health and beauty aids that can include the cationically andhydrophilically modified polymer composition of this invention (e.g., asspreading aids and film formers) include, without being limited thereto,skin protective spray, cream, lotion, gel, stick and powder products,such as insect repellants, itch relief, antiseptics, disinfectants, sunblocks, sun screens, skin tightening and toning milks, and lotions, wartremoval compositions, and the like.

In a given composition or application, the cationically andhydrophilically modified Cassia polymers of this invention can, but neednot, serve more than one function, such as a fixative, thickener, skinand hair conditioner, film former and carrier or deposition aid. In apersonal care composition, the amount of cationically andhydrophilically modified Cassia polymer that can be employed dependsupon the purpose for which they are included in the formulation and canbe determined by person skilled in the formulation art. Thus, as long asthe desired physicochemical and functional properties are achieved, auseful amount of cationically and hydrophilically modified Cassiapolymer on a total composition weight basis, typically can vary in therange of from about 0.01% to about 50% in one aspect of the invention,from about 0.1 wt. % to about 35 wt. % in another aspect, from about 0.2wt. % to about 25 wt. % in a further aspect, and from 1 to about 10 wt.% in a still further aspect of the invention, based on the total weightof the composition, but is not limited thereto.

The cationically and hydrophilically modified Cassia polymers of theinvention can be employed as conditioners and/or deposition aids in hairfixative and styling shampoo compositions. In addition, they can beemployed as a fixative agent in a hair fixative composition. Thecationically and hydrophilically modified Cassia polymer can be used inshampoos and conditioners to facilitate combability. The positivelycharged nitrogen atom interacts with the negatively charged hair fibersto form films. They also make the hair feel softer and smoother to thetouch without creating excessive residual build-up. The cationically andhydrophilically modified Cassia polymers can be used as part of aconditioner package in a conditioning detersive formulation that notonly imparts cleansing, wet detangling, dry detangling and manageabilityattributes to the hair, but also is relatively non-irritating. Thiscomposition is thus suitable for use by young children and adults havingsensitive skin and eyes. In addition, cationically and hydrophilicallymodified Cassia polymer has been found to be an excellent deposition aidin the deposition of conditioning and therapeutic agents to the hair.

As is discussed herein, the cationically and hydrophilically modifiedCassia polymers of the present invention permit, facilitate and/orenhance the delivery, deposition and/or activity of one or more activeingredients utilized in a personal care, home care, health care, andinstitutional care formulations, and for improving the psychosensory andaesthetic properties of a topical formulation in which they areincluded. Examples of such active ingredients include, but are notlimited to, caffeine, vitamin C, vitamin D, vitamin E, anti-stretch markcompounds, astringents (e.g., alum, oatmeal, yarrow, witch hazel,bayberry, and isopropyl alcohol), draining compounds, hair growthpromoting compounds (e.g., monoxidil), skin and hair nourishingcompounds, skin and hair protecting compounds, self-tanning compounds(e.g., mono- or polycarbonyl compounds such as, for example, isatin,alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde,glutaraldehyde, erythrulose, tyrosine, tyrosine esters, anddihydroxyacetone), sunscreens (e.g., ethylhexyl methoxy cinnamate,octinoxate, octisalate, oxybenzone), skin lighteners (e.g., kojic acid,hydroquinone, arbutin, fruital, vegetal or plant extracts, such as lemonpeel extract, chamomile, green tea, paper mulberry extract, and thelike, ascorbyl acid derivatives, such as ascorbyl palmitate, ascorbylstearate, magnesium ascorbyl phosphate, and the like), lip plumpingcompounds, anti-aging, anti-cellulite, and anti-acne compounds (e.g.,acidic agents such as alpha-hydroxy acids (AHAs), beta-hydroxy acids(BHAs), alpha amino-acids, alpha-keto acids (AKAs), acetic acid, azelaicacid, and mixtures thereof), anti-dandruff compounds (e.g., zincpyrithione, zinc omadine, miconazole nitrate, selenium sulfide,piroctone olamine) anti-inflammatory compounds (e.g., aspirin,ibuprofen, and naproxen), analgesics (e.g., acetaminophen), antioxidantcompounds, antiperspirant compounds (e.g., aluminum halides, aluminumhydroxyhalides, aluminum sulfate, zirconium (zirconyl) oxyhalides,zirconium (zirconyl)hydroxyhalides, and mixtures or complexes thereof),deodorant compounds (e.g., 2-amino-2-methyl-1-propanol (AMP), ammoniumphenolsulfonate; benzalkonium chloride; benzethonium chloride,bromochlorophene, cetyltrimethylammonium bromide, cetyl pyridiniumchloride, chlorophyllin-copper complex, chlorothymol, chloroxylenol,cloflucarban, dequalinium chloride, dichlorophene, dichloro-m-xylenol,disodium dihydroxyethyl sulfosuccinylundecylenate, domiphen bromide,hexachlorophene, lauryl pyridinium chloride, methylbenzethoniumchloride, phenol, sodium bicarbonate, sodium phenolsulfonate,triclocarban, triclosan, zinc phenolsulfonate, zinc ricinoleate, andmixtures thereof), hair fixative polymers (e.g., natural and syntheticpolymers such as, for example, polyacrylates, polyvinyls, polyesters,polyurethanes, polyamides, modified cellulose, starches, and mixturesthereof), hair and skin conditioners (e.g., synthetic oils, naturaloils, such as vegetable, plant and animal oils, mineral oils, naturaland synthetic waxes, cationic polymers, monomeric and polymericquaternized ammonium salt compounds, silicones such as silicone oils,resins and gums, proteins, hydrolyzed proteins, fatty acids, fattyamines; and mixtures thereof); and suitable mixtures of two or more ofthe above.

The cationically and hydrophilically modified Cassia polymercompositions of this invention are particularly useful as depositionaids for particulates, such as mica, pearlizing agents, beads, and thelike, making them suitable for dermal products containing particulates,microabrasives, and abrasives, such as shower gels, masks and skincleansers containing exfoliating agents. Numerous cosmetically usefulparticulate exfoliating agents are known in the art, and the selectionand amount is determined by the exfoliating effect desired from the useof the composition, as recognized by those skilled in the cosmetic arts.Useful exfoliating agents include, but are not limited to, biologicalabrasives, inorganic abrasives, synthetic polymers, and the like, andmixtures thereof. Biological abrasives include, without limitation,shell, seed, and kernel or stone granules or powders, obtained fromnuts, such as from walnut (Juglans regia) shells, almonds, pecans, andthe like; fruit sources, such as apricots, avocados, coconuts, olives,peaches, and the like; vegetal sources, such as corn cob, oat bran,rice, rose hip seed, jojoba (wax, seed powder), microcrystallinecellulose, ground loofa, ground seaweed, and the like; animal sources,such as oyster shell, silk, microcrystalline collagen, and the like.Inorganic abrasives include, without limitation, stannic oxide, talc,silica (hydrated, colloidal and the like), kaolin, precipitated chalk,salts (sodium chloride, dead sea salt, and the like), ground pumice, andthe like. Synthetic polymers include, without limitation,microcrystalline polyamides (nylons), microcrystalline polyesters(polycarbonates), and the like.

The cationically and hydrophilically modified Cassia polymers of thisinvention are useful as thickeners and film-formers in a variety ofdermatological, cosmeceutical compositions employed for topicallyameliorating skin conditions caused by drying, photo-damage, aging,acne, and the like, containing conditioners, moisturizers, antioxidants,keratolytic agents, vitamins, and the like, typically containing anactive acidic ingredient and having a pH in the range of about 0.5 toabout 5.

In one cosmeceutical aspect, the cationically and hydrophilicallymodified Cassia polymers of this invention can be employed as athickener or deposition aid for active skin treatment lotions and creamscontaining, as active ingredients, acidic anti-aging, anti-cellulite,and anti-acne agents, hydroxy carboxylic acids, such as alpha-hydroxyacid (AHA), beta-hydroxy acid (BHA), alpha-amino acid, alpha-keto acids(AKAs), and mixtures thereof. In such cosmeceuticals, AHAs can include,but are not limited to, lactic acid, glycolic acid, fruit acids, such asmalic acid, citric acid, tartaric acid, extracts of natural compoundscontaining AHA, such as apple extract, apricot extract, and the like,honey extract, 2-hydroxyoctanoic acid, glyceric acid (dihydroxypropionicacid), tartronic acid (hydroxypropanedioic acid), gluconic acid,mandelic acid, benzilic acid, azelaic acid, alpha-lipoic acid, salicylicacid, AHA salts and derivatives, such as arginine glycolate, ammoniumglycolate, sodium glycolate, arginine lactate, ammonium lactate, sodiumlactate, alpha-hydroxybutyric acid, alpha-hydroxyisobutyric acid,alpha-hydroxyisocaproic acid, alpha-hydroxyisovaleric acid, atrolacticacid, and the like. BHAs can include, but are not limited to, 3-hydroxypropanoic acid, beta-hydroxybutyric acid, beta-phenyl lactic acid,beta-phenylpyruvic acid, and the like. Alpha-amino acids include,without being limited thereto, alpha-amino dicarboxylic acids, such asaspartic acid, glutamic acid, and mixtures thereof, sometimes employedin combination with fruit acid. AKAs include pyruvic acid. In someantiaging compositions, the acidic active agent may be retinoic acid, ahalocarboxylic acid, such as trichloroacetic acid, an acidicantioxidant, such as ascorbic acid (vitamin C), a mineral acid, phyticacid, lysophosphatidic acid, and the like. Some acidic anti-acneactives, for example, can include salicylic acid, derivatives ofsalicylic acid, such as 5-octanoylsalicylic acid, retinoic acid, and itsderivatives.

A discussion of the use and formulation of active skin treatmentcompositions is in Cosmetics & Toiletries®, C&T Ingredient ResourceSeries, “AHAs & Cellulite Products How They Work”, published 1995, and“Cosmeceuticals”, published 1998, both available from Allured PublishingCorporation, incorporated herein by reference. Compositions containingalpha-amino acids acidified with ascorbic acid are described in U.S.Pat. No. 6,197,317 B1, and a commercial cosmeceutical preparationutilizing these acids in an anti-aging, skin care regimen is sold underthe tradename, AFAs, by exCel Cosmeceuticals (Bloomfield Hills, Mich.).The term “AFA”, as described in the supplier's trade literature, wascoined by the developer to describe the amino acid/vitamin C combinationas Amino Fruit Acids and as the acronym for “Amino acid Filaggrin basedAntioxidants.”

Other health care products in which cationically and hydrophilicallymodified Cassia polymers can be included are medical products, such astopical and non-topical pharmaceuticals, and devices. In the formulationof pharmaceuticals, the cationically and hydrophilically modifiedpolymer composition of this invention can be employed as a thickenerand/or lubricant in such products as creams, pomades, gels, pastes,ointments, tablets, gel capsules, purgative fluids (enemas, emetics,colonics, and the like), suppositories, anti-fungal foams, eye products(ophthalmic products, such as eye drops, artificial tears, glaucoma drugdelivery drops, contact lens cleaner, and the like), ear products (waxsofteners, wax removers, otitis drug delivery drops, and the like),nasal products (drops, ointments, sprays, and the like), and wound care(liquid bandages, wound dressings, antibiotic creams, ointments, and thelike), without limitation thereto.

The film-forming cationically and hydrophilically modified Cassiapolymers of this invention make them particularly suitable as a vehiclefor topical medical compositions for promoting and enhancing thetransdermal delivery of active ingredients to or through the skin, forenhancing the efficacy of anti-acne agents formulations and topicalanalgesics, and for controlling release of drugs, such as antacids fromtablets, or syrups, at low pH, such as in the stomach; controlling drugrelease from tablets, lozenges, chewables, and the like in the mildlyacidic environment of the mouth; or from suppositories, ointments,creams, and the like in the mildly acidic environment of the vagina; topromote deposition of dandruff control agents from shampoos, salves, andthe like; to enhance the deposition of colorants on skin from pigmentedcosmetics (makeups, lipsticks, rouges, and the like) and on hair fromhair dyes, and the like.

In addition to the foregoing, the cationic character of the Cassiapolymers of the present invention and its cationic compatibility makesthe polymer useful as a thickener or deposition aid for antistatic,biocidal, antimicrobial, and other preservative compositions, in avariety of personal care, health care, I&I, and medical applications.For example, the polymer can be employed as a thickener inover-the-counter (OTC) health care and pharmaceutical products wherecationic biocides are typically employed, such as in oral carecompositions for plaque and tartar control, and liquid vehiclescontaining therapeutic agents, such as syrups, gels, and the like. Undercertain controlled pH conditions, the cationic character of thecationically and hydrophilically modified polymer composition of thisinvention, itself, may also provide antistatic activity or biocidal,antimicrobial, or like preservative activity.

The cationically and hydrophilically modified Cassia polymers of thepresent invention can be employed, without limitation, as a lubricantcoating for medical devices, such as soft tissue implants, surgicalgloves, catheters, cannulae, and the like, as removable protective filmcoatings for medical instruments, wound dressings, and the like, as amuco-adhesive, especially in the acid environment of the stomach, as acarrier and thickener in formulated products for medical applications,such as disinfectant hand creams, antiviral products (for anionicviruses), antibiotic ointments, sprays and creams, non-drip, sprayabledisinfectant in hospitals, hard surface antimicrobial finish appliedduring routine maintenance, and the like.

The cationically and hydrophilically modified Cassia polymers of thepresent invention can be used in home care, and I&I applications, forexample, as a rheology modifier, fabric conditioning agent, antistaticagent, especially to improve formulation efficiency through“cling-on-surface” or improving efficacy of disinfectants, and biocidalformulations, and to synergistically improve fabric softening efficacyin combination with traditional fabric softeners. Typical household andI&I products that may contain polymers of the invention, include,without being limited thereto, laundry and fabric care products, such asdetergents, fabric softeners (liquids or sheets), ironing sprays, drycleaning aids, anti-wrinkle sprays, spot removers and the like; hardsurface cleansers for the kitchen and bathroom and utilities andappliances employed or located therein, such as toilet bowl gels, tuband shower cleaners, hard water deposit removers, floor and tilecleansers, wall cleansers, floor and chrome fixture polishes,alkali-strippable vinyl floor cleaners, marble and ceramic cleaners, airfreshener gels, liquid cleansers for dishes, and the like; disinfectantcleaners, such as toilet bowl and bidet cleaners, disinfectant handsoaps, room deodorizers, and the like.

The cationically and hydrophilically modified Cassia polymers of thepresent invention can be utilized as rheology modifiers, dispersants,stabilizers, promoters, or antimicrobials, and the like, in industrialproduct applications, such as, without being limited thereto, textiles(processing, finishing, printing, and dyeing aids, protective washablesurface coatings, manufacture of synthetic leather by saturation ofnon-woven fabrics, and the like, manufacturing of woven fabrics,non-woven fabrics, natural and synthetic fibers and the like); watertreatments (waste water, cooling water, potable water purification, andthe like); chemical spill containments (acid-spill absorbent, and thelike); leather and hide processing (processing aids, finishing, coating,embossing, and the like); paper and papermaking (surface coatings, suchas pigmented coatings, antistatic coatings, and the like, pulp binders,surface sizings, dry and wet strength enhancers, manufacture of wet-laidfelts, and the like); printing (inks, anti-wicking ink-jet printer inks,thickeners for ink formulations containing cationic dyes for printingacrylic fabrics, and the like); paints (pigment and grinding additive);industrial plant effluent treatment (flocculents for phenolics in papermill effluent, and the like); metal working (acid etch cleaners, low pHmetal coatings, pickling agents in cold rolled steel processing, and thelike); adhesives (clear adhesives, adhesion promoters for metal,plastic, wood, and the like, non-woven floc adhesive tie coatings,bonding, and the like); wood preservation; and industrial constructionproducts for buildings and roads (cement plasticizers, asphalt emulsionstabilizers at low pH, acid etch for cement, consistency modifiers ofconcrete, mortar, putty, and the like). The polymers of the presentinvention are particularly useful as thickeners for rust removers, acidtruck cleaners, scale removers, and the like, and as dispersionstabilizers of products containing particulates, such as clay, pigments(titanium dioxide, calcium carbonate, and other minerals), abrasives,and the like, employed in a variety of the foregoing industrialapplications, and in drilling muds.

Products containing cationically and hydrophilically modified Cassiapolymers of the present invention can contain various conventionaladditives and adjuvants known in the art, some of which can serve morethan one function. The amounts employed will vary with the purpose andcharacter of the product and can be readily determined by one skilled inthe formulation arts and from the literature. The term “cosmeticadjuvant” includes cosmetically and pharmaceutically acceptable productstabilizing and product finishing agents that maintain the physicalstability of the composition and its visible aesthetic appearance andmarket appeal during the useful shelf life of the composition.

The term “fixative” as applied to polymers encompasses the properties offilm-formation, adhesion, or coating deposited on a surface on which thepolymer is applied. The terms “hair styling and hair fixative” ascommonly understood in the hair care arts, and as used herein, refercollectively to hair setting agents that are hair fixatives and filmformers and which are topically applied to the hair to activelycontribute to the ease of styling and/or holding of a hair set, and tomaintain the restylability of the hair set. Hence, hair settingcompositions include hair styling, hair fixative, and hair groomingproducts that conventionally are applied to the hair (wet or dry) in theform of gels, rinses, emulsions (oil-in-water, water-in-oil ormultiphase), such as lotions and creams, pomades, sprays (pressurized ornon-pressurized), spritzes, foams, such as mousses, shampoos, solids,such as sticks, semisolids and the like, or are applied from a hairsetting aid having the hair setting composition impregnated therein orcoated thereon, to leave the hair setting agent in contact on the hairfor some period until removed, as by washing.

The term “conditioning agents”, and grammatical variations thereof, asit relates to compositions for skin care and hair care includescosmetically and pharmaceutically useful materials that can function ashumectants, moisturizers, and emollients. It is recognized that someconditioning agents can serve more than one function in a composition,such as an emulsifying agent, a lubricant, and/or a solvent.Conditioning agents include any material which is used to give aparticular conditioning benefit to hair and/or skin. In hair treatmentcompositions, suitable conditioning agents are those which deliver oneor more benefits relating to shine, softness, combability, antistaticproperties, wet-handling, damage repair, manageability, detangling,body, and lubricity. Suitable conditioning agents for use in personalcleansing compositions are those conditioning agents characterizedgenerally as silicones (e.g. silicone fluids, silicone oils, cationicsilicones, silicone gums, high refractive silicones, silicone resins,emulsified silicones, and dimethicone copolyols), organic conditioningoils (e.g. hydrocarbon oils, natural oils, polyolefins, and fattyesters), natural and synthetic waxes, fatty esters, cationic polymers(including polyquaternium polymers), monomeric quaternary ammoniumcompounds, and combinations thereof.

A preferred hair care composition embodiment comprises a cationicallyand hydrophilically modified Cassia polymer of the present invention inan amount effective to provide to the hair care composition a property,such as a hair fixative property, a hair conditioning property, a viscidproperty (thickening, rheology modifying), or a combination thereof.Optionally, the hair care composition can include one or more auxiliaryfilm-forming agent, auxiliary hair-fixative agent, auxiliary hairconditioning agent, auxiliary rheology modifying agent, propellants, anda combination thereof.

A preferred skin care composition embodiment comprises a cationicallyand hydrophilically modified Cassia polymer of the present invention inan amount effective to provide to the skin care composition a property,such as a skin conditioning property, a viscid property (thickening,rheology modifying), or a combination thereof. Optionally, the skin carecomposition can include one or more auxiliary skin conditioning agent,auxiliary rheology modifying agent, or a mixture thereof.

Product formulations comprising a cationically and hydrophilicallymodified Cassia polymer of this invention can contain various additivesand cosmetic adjuvants, conventionally or popularly included in personalcare, household care, institutional care, and industrial care products,and in industrial processes, including, without being limited thereto,acidifying or alkalizing pH adjusting agents (neutralizing agents) andbuffering agents; auxiliary fixatives and film formers, such asnonionic, anionic, cationic, or amphoteric polymers of synthetic ornatural origin, and the like; auxiliary rheology modifiers, such asviscosity-increasing polymeric, gum, or resin thickeners or gellants;additives, such as emulsifiers, emulsion stabilizers, waxes,dispersants, and the like, and viscosity control agents, such assolvents, electrolytes, and the like; auxiliary conditioning agents,such as antistatic agents, synthetic oils, vegetable or animal oils,silicone oils, monomeric or polymeric quaternized ammonium compounds andderivatives thereof, sheen enhancers, moisturizers, emollients,humectants, lubricants, sunscreen agents, and the like; oxidizingagents; reducing agents; surfactants, such as anionic, cationic,nonionic, amphoteric, zwitterionic surfactants, and silicone derivativesthereof; polymer film modifying agents, such as plasticizers,tackifiers, detackifiers, wetting agents, and the like; productstabilizing and finishing agents, such as chelating agents, opacifiers,pearlescing agents, proteinaceous materials and derivatives thereof,vitamins and derivatives thereof, preservatives, fragrances,solubilizers, colorants (temporary or permanent), such as pigments anddyes, UV absorbers, and the like; propellants (water-miscible orwater-immiscible), such as fluorinated hydrocarbons, liquid volatilehydrocarbons, compressed gases, and the like; and mixtures thereof.

Additives and adjuvant ingredients, products, or materials, which may beemployed with the inventive cationically and hydrophilically modifiedpolymer composition discussed herein will be referred to by theinternational nomenclature commonly referred to as INCI name given themin the International Cosmetic Ingredient Dictionary, published by thePersonal Care Products Council (formally the Cosmetic, Toiletry, andFragrance Association), Washington D.C. (hereafter INCI Dictionary),such as can be found in any edition thereof, for example, Volumes 1 and2, Sixth Edition, (1995) or Volumes 1-3, Seventh and Eighth Editions,(1997, 2000), or by their commonly used chemical names. Numerouscommercial suppliers of materials listed by INCI name, trade name orboth can be found in the INCI Dictionary and in numerous commercialtrade publications, including but not limited to the 2001 McCutcheon'sDirectories, Volume 1: Emulsifiers & Detergents and Volume 2: FunctionalMaterials, published by McCutcheon's Division, The ManufacturingConfectioner Publishing Co., Glen Rock, N.J. (2001); and 2001 CosmeticBench Reference, edition of Cosmetics & Toiletries®, 115 (13), publishedby Allured Publishing Corporation, Carol Stream, Ill. (2001); therelevant disclosures of each are incorporated herein by reference. Suchcomponents and the formulation of compositions are also described indetail in well known references, such as Cosmetics Science andTechnology, First Edition (Sagarin (ed)), published 1957, and SecondEdition (Balsam, et al. (eds)), published 1972-74; and The Chemistry andManufacture of Cosmetics, Second Edition (deNavarre (ed)), published1975, and Third Edition (Schlossman (ed)), published 2000, bothavailable from Allured Publishing Corporation; Rieger (ed), Harry'sCosmeticology, 8th Edition, Chemical Publishing, Co., Inc., New York,N.Y. (2000); and various formularies available to those skilled in thepharmaceutical arts, such as Remington's Pharmaceutical Sciences,Fourteenth Edition, Mack Publishing Company, Easton, Pa. (1970); therelevant disclosures of each are incorporated herein by reference.

It is known that formulated compositions for personal care and topical,dermatological, health care, which are applied to the skin and mucousmembranes for cleansing or soothing, are compounded with many of thesame or similar physiologically tolerable ingredients and formulated inthe same or similar product forms, differing primarily in the puritygrade of ingredient selected, by the presence of medicaments orpharmaceutically accepted compounds, and by the controlled conditionsunder which products may be manufactured. Likewise, many of theingredients employed in products for households, and I&I are the same orsimilar to the foregoing, differing primarily in the amounts andmaterial grade employed. It is also known that the selection andpermitted amount of ingredients also may be subject to governmentalregulations, on a national, regional, local, and international level.Thus, discussion herein of various useful ingredients for personal careand health care products may apply to household and I&I products andindustrial applications.

The choice and amount of ingredients in formulated compositionscontaining the cationically and hydrophilically modified Cassia polymersof this invention will vary depending on the product and its function,as is well known to those skilled in the formulation arts. Formulationingredients for personal care and topical health care products typicallycan include, but are not limited to, solvents, surfactants (as cleansingagents, emulsifying agents, foam boosters, hydrotropes, solubilizingagents, and suspending agents), non-surfactant suspending agents,emulsifiers, skin conditioning agents (emollients, humectants,moisturizers, and the like), hair conditioning agents, hair fixatives,film-formers, skin protectants, binders, chelating agents, antimicrobialagents, antifungal agents, antidandruff agents, abrasives, adhesives,absorbents, dyes, deodorant agents, antiperspirant agents, opacifyingand pearlescing agents, antioxidants, preservatives, propellants,spreading aids, sunscreen agents, sunless skin tanning accelerators,ultraviolet light absorbers, pH adjusting agents, botanicals, haircolorants, oxidizing agents, reducing agents, hair and skin bleachingagents, pigments, physiologically active agents, anti-inflammatoryagents, topical anesthetics, fragrance and fragrance solubilizers, andthe like, in addition to ingredients previously discussed that may notappear herein. Oral care products, for example, can contain anticaries,anti-tartar and/or anti-plaque agents in addition to surfactants,abrasives, humectants, and flavorants. An extensive listing ofsubstances and their conventional functions and product categoriesappears in the INCI Dictionary, generally, and in Vol. 2, Sections 4 and5 of the Seventh Edition, in particular, incorporated herein byreference.

The cationically and hydrophilically modified Cassia polymers of thepresent invention are particularly useful for water-based, solventbased, hydroalcoholic based, and mixed solvent formulations, and forformulations containing water-miscible auxiliary solvents, but are notlimited thereto. Useful solvents commonly employed are typicallyliquids, such as water (deionized, distilled or purified), polyols, andthe like, and mixtures thereof. Non-aqueous or hydrophobic auxiliarysolvents are commonly employed in substantially water-free products,such as nail lacquers, aerosol propellant sprays, or for specificfunctions, such as removal of oily soils, sebum, make-up, or fordissolving dyes, fragrances, and the like, or are incorporated in theoily phase of an emulsion. Non-limiting examples of auxiliary solvents,other than water, include linear and branched C₁-C₆ alcohols, such asethanol, propanol, isopropanol, butanol, hexanol, and mixtures thereof;aromatic alcohols, such as benzyl alcohol, cycloaliphatic alcohols, suchas cyclohexanol, and the like; saturated C₁₂-C₃₀ fatty alcohol, such aslauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol,behenyl alcohol, and the like. Non-limiting examples of polyols includepolyhydroxy alcohols, such as glycerin, propylene glycol, butyleneglycol, hexylene glycol, C₂-C₄ alkoxylated alcohols and C₂-C₄alkoxylated polyols, such as ethoxylated, propoxylated, and butoxylatedethers of alcohols, diols, and polyols having about 2 to about 30 carbonatoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutyleneglycol, and the like. Non-limiting examples of non-aqueous auxiliarysolvents include silicones, and silicone derivatives, such ascyclomethicone, and the like, aliphatic solvents such as cyclohexane andheptane, ketones such as acetone and methyl ethyl ketone, and mixturesthereof; ethers such as dimethyl ether, dimethoxymethane, and mixturesthereof, natural and synthetic oils and waxes, such as vegetable oils,plant oils, animal oils, essential oils, mineral oils, C₇-C₄₀isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amylacetate, ethyl lactate, and the like, jojoba oil, shark liver oil, andthe like. Mixtures of the foregoing solvents can also be utilized incombination with the cationically and hydrophilically modified Cassiapolymers of the invention. Some of the foregoing non-aqueous auxiliarysolvents may also function as conditioners and emulsifiers.

Surfactants are generally employed as cleansing agents, emulsifyingagents, foam boosters, hydrotropes and suspending agents. Thecationically and hydrophilically modified Cassia polymers of the presentinvention may be employed in formulations containing all classes ofsurfactants, i.e., anionic surfactants, cationic surfactants, nonionicsurfactants, amphoteric surfactants. The term “amphoteric surfactant” asused herein includes zwitterionic surfactants. In addition to theforegoing references, discussions of the classes of surfactants are inCosmetics & Toiletries® C&T Ingredient Resource Series, “SurfactantEncyclopedia”, 2nd Edition, Rieger (ed), Allured Publishing Corporation(1996); Schwartz, et al., Surface Active Agents, Their Chemistry andTechnology, published 1949; and Surface Active Agents and Detergents,Volume II, published 1958, Interscience Publishers; each incorporatedherein by reference.

Surprisingly, the cationically and hydrophilically modified Cassiapolymers of the present invention are useful as thickeners anddeposition aids in compositions containing a relatively highconcentration (about 10-40 weight percent) of anionic surfactant, suchas shampoos and two-in-one type liquid conditioning/cleansers for hairand body (bath) products.

Anionic surfactants include substances having a negatively chargedhydrophobe or that carry a negative charge when the pH is elevated toneutrality or above, such as acylamino acids, and salts thereof, forexample, acylglutamates, acyl peptides, sarcosinates, and taurates;carboxylic acids, and salts thereof, for example, alkanolic acids andalkanoates, ester carboxylic acids, and ether carboxylic acids;phosphoric acid ester and salts thereof; sulfonic acids and saltsthereof, for example, acyl isethionates, alkylaryl sulfonates, alkylsulfonates, and sulfosuccinates; and sulfuric acid esters, such as alkylether sulfates and alkyl sulfates.

Non-limiting examples of anionic surfactants include mono-basic salts ofacylglutamates that are slightly acidic in aqueous solution, such assodium acylglutamate and sodium hydrogenated tallow glutamate; salts ofacyl-hydrolyzed protein, such as potassium, palmitoyl hydrolyzed milkprotein, sodium cocoyl hydrolyzed soy protein, and TEA-abietoylhydrolyzed collagen; salts of acyl sarcosinates, such as ammoniummyristoyl sarcosine, sodium cocoyl sarcosinate, and TEA-lauroylsarcosinate; salts of sodium methyl acyltaurates, such as sodium lauroyltaurate and sodium methyl cocoyl taurate; alkanoic acids and alkanoates,such as fatty acids derived from animal and vegetable glycerides thatform water-soluble soaps and water-insoluble emulsifying soaps,including sodium stearate, aluminum stearate, and zinc undecylenate;ester carboxylic acids, such as dinonoxynol-9-citrate; salts of acyllactylates such as calcium stearoyl lactylate and laureth-6 citrate;ethercarboxylic acids derived from ethyoxylated alcohols or phenolshaving varying lengths of polyoxyethylene chains, such as nonoxynol-8carboxylic acid, and sodium trideceth-13 carboxylate; mono- anddi-esters of phosphoric acid and their salts, such as phospholipids,dilaureth-4-phosphate, DEA-oleth-10 phosphate and triethanolamine laurylphosphate; salts of acylisethionate, such as sodium cocoyl isethionate;alkylarylbenzene sulfonates, such as alpha-olefin sulfonate (AOS) andalkali metal, alkaline earth metal, and alkanolamine salts thereof, andsodium dodecylbenzene sulfonate; alkyl sulfonates, such as sodiumC₁₂-C₁₄ olefin sulfonate, sodium cocomonoglyceride sulfonate, sodiumC₁₂-C₁₅ pareth-15 sulfonate, and sodium lauryl sulfoacetate;sulfosuccinates, such as mono- and di-esters of sulfosuccinic acid,salts thereof and alkoxylated alkyl and alkylamido derivatives thereof,such as di-C₄-C₁₀ alkyl sodium sulfosuccinate, disodium laurethsulfosuccinate, disodium oleamido MEA-sulfosuccinate, and disodiumC₁₂-C₁₅ pareth sulfosuccinate; alkyl ether sulfates, such as sodium andammonium lauryl ether sulfate (having about 1 to about 12 moles ethyleneoxide); alkyl sulfates, such as sodium, ammonium and triethanolaminesalts of C₁₂-C₁₈ alkylsulfates, sodium C₁₂-C₁₄ olefin sulfates, sodiumlaureth-6 carboxylate, sodium C₁₂-C₁₈ pareth sulfate, and the like.

Cationic surfactants can have a hydrophobe that carries a positivecharge or that is uncharged at pH values close to neutrality or lower,such as alkylamines, alkyl imidazolines, ethoxylated amines, andquaternary ammonium compounds. Cationic surfactants used in cosmeticsare preferably N-derivatives and the neutralizing anion may be inorganicor organic. Among the cationic surfactant materials useful herein arequaternary ammonium compounds corresponding to the general formula:(R¹⁰R¹¹R¹²R¹³N⁺) E⁻, wherein each of R¹⁰, R¹¹, R¹², and R¹³ areindependently selected from an aliphatic group having from 1 to about 22carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido,hydroxyalkyl, aryl or alkylaryl group having 1 to about 22 carbon atomsin the alkyl chain; and E is a salt-forming anion such as those selectedfrom halogen, (e.g. chloride, bromide), acetate, citrate, lactate,glycolate, phosphate, nitrate, sulfate, and alkylsulfate. The aliphaticgroups can contain, in addition to carbon and hydrogen atoms, etherlinkages, ester linkages, and other groups such as amino groups. Thelonger chain aliphatic groups, e.g., those of about 12 carbons, orhigher, can be saturated or unsaturated.

Alkylamines can be salts of primary, secondary and tertiary fattyC₁₂-C₂₂ alkylamines, substituted or unsubstituted, and substancessometimes referred to as “amidoamines”. Non-limiting examples ofalkylamines and salts thereof include dimethyl cocamine, dimethylpalmitamine, dioctylamine, dimethyl stearamine, dimethyl soyamine,soyamine, myristyl amine, tridecyl amine, ethyl stearylamine,N-tallowpropane diamine, ethoxylated stearylamine, dihydroxy ethylstearylamine, arachidylbehenylamine, dimethyl lauramine, stearylaminehydrochloride, soyamine chloride, stearylamine formate, N-tallowpropanediamine dichloride, and amodimethicone (INCI name for a silicone polymerand blocked with amino functional groups, such as aminoethylaminopropylsiloxane). Non-limiting examples of amidoamines and salts thereofinclude stearamido propyl dimethyl amine, stearamidopropyl dimethylaminecitrate, palmitamidopropyl diethylamine, and cocamidopropyldimethylamine lactate. Other cationic surfactants includedistearyldimonium chloride, dicetyldimonium chloride, guarhydroxypropyltrimonium chloride, and the like. At low pH, amine oxidesmay protonate and behave similarly to N-alkyl amines.

Non-limiting examples of alkyl imidazolines include alkyl hydroxyethylimidazoline, such as stearyl hydroxyethyl imidazoline, coco hydroxyethylimidazoline, ethyl hydroxymethyl oleyl oxazoline, and the like.Non-limiting examples of ethyoxylated amines include PEG-cocopolyamine,PEG-15 tallow amine, quaternium-52, and the like.

Quaternary ammonium compounds can be selected from monomeric orpolymeric materials containing at least one nitrogen atom that is linkedcovalently to four alkyl and/or aryl substituents, and the nitrogen atomremains positively charged regardless of the environmental pH.Quaternary ammonium compounds comprise a large number of substances thatare used extensively as surfactants, conditioners, antistatic agents,and antimicrobial agents and include, alkylbenzyldimethyl ammoniumsalts, alkyl betaines, heterocyclic ammonium salts, andtetraalkylammonium salts. Long-chain (fatty) alkylbenzyldimethylammonium salts are preferred as conditioners, as antistatic agents, andas fabric softeners, discussed in more detail below. Other quaternaryammonium compounds include quaternary ammonium silicones. While variousquaternary ammonium compounds are listed for a specific purpose, one ofordinary skill will recognize that the quaternary ammonium compoundsdescribed here and throughout the specification can serve more than onefunction.

Non-limiting examples of alkylbenzyldimethylammonium salts includestearalkonium chloride, benzalkonium chloride, quaternium-63,olealkonium chloride, didecyldimonium chloride, and the like. Alkylbetaine compounds include alkylamidopropyl betaine, alkylamidopropylhydroxysultaine, and sodium alkylamido propyl hydroxyphostaine.Non-limiting examples of alkyl betaine compounds include oleyl betaine,coco-betaine, cocoamidopropyl betaine, coco-hydroxy sultaine,coco/oleamidopropyl betaine, coco-sultaine, cocoamidopropylhydroxysultaine, and sodium lauramidopropyl hydroxyphostaine. Heterocyclicammonium salts include alkylethyl morpholinium ethosulfate, isostearylethylimidonium ethosulfate, and alkylpyridinium chlorides, and aregenerally used as emulsifying agents. Non-limiting examples ofheterocyclic ammonium salts include cetylpyridinium chloride,isostearylethylimidonium ethosulfate, and the like. Non-limitingexamples of tetraalkylammonium salts include cocamidopropylethyldimonium ethosulfate, hydroxyethyl cetyldimonium chloride,quaternium-18, and cocodimonium hyroxypropyl hydrolyzed protein, such ashair keratin, and the like.

The cationically and hydrophilically modified Cassia polymers of thepresent invention are surprisingly compatible with cationic surfactantsand other cationic compounds suitable as antistatic agents, such asthose employed in hair care and fabric care products. The term“antistatic agents” as used herein refers to ingredients that alter theelectrical properties of cosmetic raw materials or of human bodysurfaces (skin, hair, etc.) and textiles, for example, by reducing theirtendency to acquire an electrical charge and thus, can condition hair,skin and fabrics. The cationic compatibility of the instant cationicallyand hydrophilically modified polymers makes them suitable forincorporation into formulations containing antistatic agents typicallyemployed in hair care compositions, such as shampoos, post-shampooconditioning rinses, hair sprays, hair dressings and the like. Theantistatic agent can be employed in amounts up to about 30 weightpercent of the final composition, but is not limited thereto.

Antistatic agents include, but are not limited to, quaternary ammoniumcompounds, protein derivatives, synthetic quaternary ammonium polymers,amines, protonated amine oxides, betaines, and the like, which may actas antistatic agents in specific formulations and under controlled pHconditions in addition to any surfactant properties imparted by suchmaterials. In addition to antistatic agents previously discussed,non-limiting examples of quaternary ammonium compounds useful asantistatic agents are acetamidopropyl trimonium chloride,behenamidopropyl dimethylamine, behenamidopropyl ethyldimoniumethosulfate, behentrimonium chloride, cetethyl morpholinium ethosulfate,cetrimonium chloride, cocoamidopropyl ethyldimonium ethosulfate,dicetyldimonium chloride, dimethicone hydroxypropyl trimonium chloride,hydroxyethyl behenamidopropyl dimonium chloride, quaternium-26,quaternium-27, quaternium-53, quaternium-63, quaternium-70,quaternium-72, quaternium-76 hydrolyzed collagen, PPG-9 diethylmoniumchloride, PPG-25 diethylmonium chloride, PPG-40 diethylmonium chloride,stearalkonium chloride, stearamidopropyl ethyl dimonium ethosulfate,steardimonium hydroxypropyl hydrolyzed wheat protein, steardimoniumhydroxypropyl hydrolyzed collagen, wheat germamidopropalkonium chloride,wheat germamidopropyl ethyldimonium ethosulfate, and the like.

Synthetic quaternary ammonium polymers, include but are not limited tofilm-forming polymers and conditioning polymers. Non-limiting examplesof synthetic quaternary ammonium polymers include polymers andcopolymers of dimethyl diallyl ammonium chloride, such aspolyquaternium-4, polyquaternium-6, polyquaternium-7, polyquaternium-22,polyquaternium-10, polyquaternium-11 polyquaternium-15,polyquaternium-16, polyquaternium-24, polyquaternium-28,polyquaternium-32, polyquaternium-33, polyquaternium-35,polyquaternium-37, polyquaternium-39, polyquaternium-44,PEG-2-cocomonium chloride, quaternium-52, and the like.

The term “hair setting composition” encompasses products comprising atleast one polymer of the present invention as a hair setting agent,which are applied to the hair (wet or dry) before, during or afterconfiguring the hair into the shape (curly or straight) desired, withoutlimitation as to product form.

The cationically and hydrophilically modified Cassia polymers of thepresent invention are surprisingly useful in hair setting and hairstyling compositions as the sole film-forming, rheology modifying,conditioning fixative agent. The cationically and hydrophilicallymodified Cassia polymers of the present invention are also useful incombination with commercially available auxiliary hair fixativepolymers, such as nonionic, cationic, and amphoteric hair settingpolymers, cationic conditioning polymers, and combinations thereof.Conventional polymeric hair fixative and hair styling polymers, wellknown in the art, include natural gums and resins and neutral or anionicpolymers of synthetic origin. Listings of commercially available hairfixative and conditioning fixative polymers can be readily found in theINCI Dictionary, in supplier websites, and in the trade literature. See,for example, the Polymer Encyclopedia published in Cosmetics &Toiletries®, 117(12), December 2002 (Allured Publishing Corporation,Carol Stream, Ill.), the relevant disclosures of which are incorporatedherein by reference.

Suitable commercially available nonionic polymers (i.e., neutral) usedas hair styling or fixative polymers include, without limitationthereto, polyvinylpyrrolidone (PVP), polyvinylpyrrolidone/vinylacetatecopolymer (PVP/VA), and the like. Commercially available cationicfixative polymers include, without limitation thereto, polymers havingthe INCI name, polyquaternium, such as polyquaternium-4, adiallyldimonium chloride/hydroxyethylcellulose copolymer (such asCELQUAT® H-100, Akzo Nobel); polyquaternium-11, a quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (such as GAFQUAT®734, 755, 755N, ISP); polyquaternium-16, a quaternized vinylpyrrolidone/vinylimidazolium chloride copolymer (such as LUVIQUAT®FC-370, BASF); polyquaternium-28, avinylpyrrolidone/methacrylamidopropyltrimethylammonium chloridecopolymer (such as GAFQUAT® HS-100, ISP); polyquaternium-46, aquaternized vinylcaprolactam/vinylpyrrolidone/methylvinylimidazoliummethosulfate copolymer; polyquaternium-55, a quaternizedvinylpyrrolidone/dimethylaminopropylmethylacrylamide/lauryldimethylpropylmethacrylamidoammoniumchloride copolymer (such as STYLEZE™ W, ISP), and the like; andamino-substituted polymers which are cationic under acidic pHconditions, such as vinylcaprolactam/PVP/dimethylaminoethylmethacrylatecopolymer (such as GAFFIX® VC-713, ISP);PVP/dimethylaminoethylmethacrylate copolymer (such as Copolymer 845,ISP), PVP/DMAPA acrylates copolymer (such as STYLEZE™ CC-10, ISP), thepyrrolidone carboxylic acid salt of chitosan, having the INCI name,Chitosan PCA (such as KYTAMER® PC, Amerchol), and the like.

Suitable amphoteric fixative polymers include, without limitationthereto, octylacryamide/acrylates/butylaminoethylmethacrylate copolymer(such as the AMPHOMER® polymers, Akzo Nobel), acrylates/laurylacrylate/stearyl acrylate/ethylamine oxide methacrylate copolymers (suchas the DIAFORMER® polymers, Clariant Corp.), and the like.

Suitable commercial conditioning polymers include polymeric quaternaryammonium salts such as, without being limited thereto, polyquaternium-7,a polymeric quaternary ammonium salt of acrylamide and dimethyldiallylammonium chloride monomers (such as MACKERNIUMTM-007, McIntyreGroup, Ltd.); polyquaternium-10, a polymeric quaternary ammonium salt ofhydroxyethylcellulose reacted with a trimethylammonium substitutedepoxide (such as the UCARE® Polymers JR, LK, LR, SR series, Amerchol andCELQUAT® SC series, Akzo Nobel); polyquaternium-39, a polymericquaternary ammonium salt of acrylic acid, diallyl dimethylammoniumchloride and acrylamide (such as the MERQUAT® and MERQUAT® Pluspolymers, Ondeo Nalco); quaternized derivatives of natural gums, e.g.,guar hydroxypropyltrimonium chloride (such as the JAGUAR® and JAGUAR®Excel polymers, Rhodia, Inc.), and the like.

A number of quaternary ammonium compounds are used for fabricconditioning and fabric care, generally referred to as fabric softeningagents, and are typically employed in amounts of up to about 20 weightpercent of the total weight of the formulation, but are not limitedthereto. Fabric softening agents useful in combination with thecationically and hydrophilically modified polymers of the presentinvention generally include long-chain alkylated quaternary ammoniumcompounds such as dialkyldimethyl quaternary ammonium compounds,imidazoline quaternary compounds, amidoamine quaternary compounds,dialkyl ester quat derivatives of dihydroxypropyl ammonium compounds;dialkyl ester quat derivatives of methyltriethanol ammonium compounds,ester amide amine compounds, and diester quat derivatives ofdimethyldiethanol ammonium chloride, as described in the review articleby Whalley, “Fabric Conditioning Agents”, HAPPI, pp. 55-58 (February1995), incorporated herein by reference.

In addition to the previously discussed antistatic agents, non-limitingexamples of dialkyldimethyl quaternary ammonium compounds, includeN,N-dioleyl-N,N-dimethylammonium chloride,N,N-ditallowyl-N,N-dimethylammonium ethosulfate,N,N-di(hydrogenated-tallowyl)-N,N-dimethylammonium chloride, and thelike. Non-limiting examples of imidazoline quaternary compounds include1-N-methyl-3-N-tallowamidoethylimidazolium chloride,3-methyl-1-tallowylamidoethyl-2-tallowylimidazolinium methylsulfate,available from Witco Chemical Company under the tradename VARISOFT® 475,and the like. Non-limiting examples of amidoamine quaternary compoundsinclude N-alkyl-N-methyl-N,N-bis(2-tallowamidoethyl)ammonium salts wherethe alkyl group can be methyl, ethyl, hydroxyethyl, and the like.Non-limiting examples of dialkyl ester quat derivatives ofdihydroxypropyl ammonium compounds include1,2-ditallowoyloxy-3-N,N,N-trimethylammoniopropane chloride,1,2-dicanoloyloxy-3-N,N,N-trimethylammoniopropane chloride, and thelike.

In addition, other types of long chain (e.g. natural oil and fattyacid-derived) alkylated quaternary ammonium compounds are suitablefabric softening agents, including, but not limited, toN,N-di(alkyloxyethyl)-N,N-dimethylammonium salts such asN,N-di(tallowyloxyethyl)-N,N-dimethylammonium chloride,N,N-di(canolyloxyethyl)-N,N-dimethylammonium chloride, and the like;N,N-di(alkyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium salts such asN,N-di(tallowyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium chloride,N,N-di(canolyloxyethyl)-N-methyl-N-(2-hydroxyethyl)ammonium chloride,and the like; N,N-di(2-alkyloxy-2-oxoethyl)-N,N-dimethylammonium salts,such as N,N-di(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride,N,N-di(2-canolyloxy-2-oxoethyl)-N,N-dimethylammonium chloride, and thelike; N,N-di(2-alkyloxyethylcarbonyloxyethyl)-N,N-dimethylammoniumsalts, such asN,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethylammoniumchloride, N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethylammoniumchloride, and the like;N-(2-alkanoyloxy-2-ethyl)-N-(2-alkyloxy-2-oxoethyl)-N,N-dimethylammonium salts, such asN-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxoethyl)-N,N-dimethylammonium chloride,N-(2-canoloyloxy-2-ethyl)-N-(2-canolyloxy-2-oxoethyl)-N,N-dimethylammonium chloride, and the like; N,N,N-tri(alkyloxyethyl)-N-methylammonium salts, such as N,N,N-tri(tallowyloxyethyl)-N-methylammoniumchloride, N,N,N-tri(canolyloxyethyl)-N-methylammonium chloride, and thelike; N-(2-alkyloxy-2-oxoethyl)-N-alkyl-N,N-dimethyl ammonium salts,such as N-(2-tallowyloxy-2-oxoethyl)-N-tallowyl-N,N-dimethyl ammoniumchloride, N-(2-canolyloxy-2-oxoethyl)-N-canolyl-N,N-dimethyl ammoniumchloride, and the like.

Preferably, the long-chain alkyl groups are derived from tallow, canolaoil, or from palm oil, however, other alkyl groups derived from soybeanoil and coconut oil, for example, are also suitable, as are lauryl,oleyl, ricinoleyl, stearyl, palmityl, and like fatty alkyl groups. Thequaternary ammonium salt compounds can have any anionic group as acounter-ion, for example, chloride, bromide, methosulfate (i.e.methylsulfate), acetate, formate, sulfate, nitrate, and the like.

Examples of preferred quaternary ammonium fabric softening compoundsinclude N-methyl-N,N-bis(tallowamidoethyl)-N-(2-hydroxyethyl)ammoniummethylsulfate andN-methyl-N,N-bis(hydrogenated-tallowamidoethyl)-N-(2-hydroxyethyl)ammonium methylsulfate, each of which materials are available from WitcoChemical Company under the trade names VARISOFT® 222 and VARISOFT® 110,respectively; dialkyl esterquat derivatives of methyltriethanol ammoniumsalts such as the DEHYQUART® AU series ofbis(acyloxyethyl)hydroxyethylmethylammonium methosulfate esterquatsavailable from Cognis, such as DEHYQUART® AU35, AU46, AU56, and thelike; and N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride, wherethe tallow chains are at least partially unsaturated. Other preferredfabric softening agents include the well-known dialkyldimethyl ammoniumsalts such as N,N-ditallowyl-N,N-dimethyl ammonium methylsulfate,N,N-di(hydrogenated-tallowyl)-N,N-dimethyl ammonium chloride,N,N-distearyl-N,N-dimethyl ammonium chloride,N,N-dibehenyl-N,N-dimethylammonium chloride, N,N-di(hydrogenatedtallow)-N,N-dimethyl ammonium chloride (trade name ADOGEN® 442),N,N-ditallowyl-N,N-dimethyl ammonium chloride (trade name ADOGEN® 470,PRAEPAGEN® 3445), N,N-distearyl-N,N-dimethyl ammonium chloride (tradename AROSURF® TA-100), all available from Witco Chemical Company;N,N-dibehenyl-N,N-dimethyl ammonium chloride, sold under the trade nameKEMAMINE® Q-2802C by Humko Chemical Division of Witco ChemicalCorporation; and N,N-dimethyl-N-stearyl-N-benzylammonium chloride soldunder the trade names VARISOFT® SDC by Witco Chemical Company andAMMONYX® 490 by Onyx Chemical Company.

Any of the foregoing fabric softening agents, and mixtures thereof, canbe utilized in combination with the cationically and hydrophilicallymodified polymers of the present invention, particularly in laundry andfabric care products. For ester-containing fabric softening agents, thepH of the compositions can influence the stability of the fabricsoftening agents, especially in prolonged storage conditions. The pH, asdefined in the present context, is measured in the neat compositions atabout 20° C. Preferably, the pH of the composition is less than about 6.For optimum hydrolytic stability of these compositions, the pH ispreferably in the range of from about 2 to about 5, more preferablyabout 2.5 to about 3.5.

Non-limiting examples of protein derivatives include cocodimoniumhydroxypropyl hydrolyzed casein, cocodimonium hydroxypropyl hydrolyzedcollagen, cocodimonium hydroxypropyl hydrolyzed hair keratin,cocodimonium hydroxypropyl hydrolyzed rice protein, cocodimoniumhydroxypropyl hydrolyzed silk, cocodimonium hydroxypropyl hydrolyzed soyprotein, cocodimonium hydroxypropyl hydrolyzed wheat protein,cocodimonium hydroxypropyl hydrolyzed silk amino acids, hydroxypropyltrimonium hydrolyzed collagen, hydroxypropyl trimonium hydrolyzedkeratin, hydroxypropyl trimonium hydrolyzed silk, hydroxypropyltrimonium hydrolyzed rice bran, hydroxypropyl trimonium hydrolyzed soyprotein, hydroxypropyl trimonium hydrolyzed vegetable protein,hydroxypropyl trimonium hydrolyzed wheat protein, hydrolyzed wheatprotein, hydrolyzed sweet almond protein, hydrolyzed rice protein,hydrolyzed soy protein, hydrolyzed milk protein, hydrolyzed vegetableprotein, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed wheatgluten, potassium cocoyl hydrolyzed collagen, hydroxypropyl trimoniumhydrolyzed collagen, cocodimonium hydroxypropyl hydrolyzed milk protein,lauryldimonium hydroxypropyl hydrolyzed wheat protein, lauryldimoniumhydroxypropyl hydrolyzed collagen, keratin amino acids, collagen aminoacids, soyethyldimonium ethosulfate, soyethyl morpholinium ethosulfate,and the like.

Nonionic surfactants are generally uncharged amphiphiles and usually arealkoxylated to varying degrees. Classes of nonionic surfactants includealcohols, alkanolamides, amine oxides, esters, and ethers. Nonionicalcohols are usually hydroxy derivatives of long-chain C₈-C₁₈ alkanehydrocarbons, such as cetearyl alcohol, hydrogenated tallow alcohol,lanolin alcohols, alkanolamides, and the like. Alkanolamides contain atleast one alkoxyl or one polyoxyethylene grouping and includealkanol-derived amides, such as acylamide DEA, N-alkyl pyrrolidone,palmamide MEA, peanutamide MIPA, and the like and ethoxylated amides,such as PEG-50 tallow amide. Amine oxides include alkylamine oxides,such as lauramine oxide; and acylamidopropyl morpholine oxides, such ascocamidopropylamine oxide; and the like. Esters include ethoxylatedcarboxylic acids, such as PEG-8 dilaurate, PEG-8 laurate, and the like;ethoxylated glycerides, such as PEG-4 castor oil, PEG-120 glycerylstearate, triolein PEG-6 esters, and the like; glycol esters andderivatives thereof, such as glycol stearate SE, propylene glycolricinoleate, and the like; monoglycerides, such as glyceryl myristate,glyceryl palmitate lactate, and the like; polyglyceryl esters, such aspolyglyceryl-6-distearate, polyglyceryl-4 oleyl ether, and the like,polyhydric alcohol esters and ethers, such as methyl gluceth-20sesquistearate, sucrose distearate; and the like; sorbitan/sorbitolesters, such as polysorbate-60, sorbitan sequiisostearate, and the like;and triesters of phosphoric acid, such as trideceth-3 phosphate,trioleth-8 phosphate, and the like. Ethers include ethoxylated alcohols,such as ceteareth-10, nonoxynol-9, and the like; ethoxylated lanolin,such as PEG-20 lanolin, PPG-12-PEG-65 lanolin oil, and the like;ethoxylated polysiloxanes, such as dimethicone copolyol, and the like;propoxylated POE ethers, such as meroxapol 314, poloxamer 122,PPG-5-ceteth-20, and the like; and alkyl polyglycosides, such as laurylglucose, and the like.

Nonionic surfactants can be used as emulsifiers, suspending agents,solubilizers, foam boosters, and in some cases, as hydrotropes.Non-limiting examples of generally preferred nonionic surfactantsinclude linear or branched alcohol ethoxylates, C₈-C₁₂ alkylphenolalkoxylates, such as octylphenol ethoxylates, polyoxyethylenepolyoxypropylene block copolymers, and the like; C₈-C₂₂ fatty acidesters of polyoxyethylene glycol mono- and di-glycerides; sorbitanesters and ethoxylated sorbitan esters; C₈-C₂₂ fatty acid glycol esters;block copolymers of ethylene oxide and propylene oxide; and the like.Non-limiting examples of surfactant foam boosters or hydrotropes includealkanolamides, such as acetamide MEA, monoethanolamide, diethanolamide,cocamide DEA, isopropanolamide, and the like; amine oxides, such ashydrogenated tallowamine oxide; short chain alkyl aryl sulfonates, suchas sodium toluene sulfonate; sulfosuccinates, such as disodium stearylsulfosuccinate; and the like.

Amphoteric and zwitterionic surfactants are those compounds that havethe capacity of behaving either as an acid or a base, by carrying apositive charge in strongly acidic media, carrying a negative charge instrongly basic media, and forming zwitterionic species at intermediatepH. The major classes of amphoteric surfactants are acyl/dialkylethylenediamines and derivatives thereof, such as disodiumcocoamphocarboxymethylhydroxy-propyl sulfate, disodiumcocamphodipropionate, sodium cocoamphoacetate, sodium lauroamphoPG-acetatephosphate, sodium tallowamphopropionate, sodiumundecylenoamphopropionate, and the like; and N-alkylamino acids, such asaminopropyl laurylglutamide, dihydroxyethyl soya glycinate,lauraminopropionic acid, and the like.

Some suitable zwitterionic surfactants for use in the presentcompositions include those broadly described as derivatives of aliphaticquaternary ammonium, phosphonium, and sulfonium compounds, wherein whichthe aliphatic radicals can be straight chain or branched, and whereinone of the aliphatic substituents contains about 8 to about 18 carbonatoms and another substituent contains an anionic water-solubilizinggroup, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, andthe like. Classes of zwitterionics include alkylamino sulfonates, alkylbetaines and alkylamido betaines, such as stearamidopropyldimethylamine,diethylaminoethylstearamide, dimethylstearamine, dimethylsoyamine,soyamine, myristylamine, tridecylamine, ethylstearylamine,N-tallowpropane diamine, ethoxylated (5 moles ethylene oxide)stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, andthe like. Some suitable betaine surfactants include but are not limitedto alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines,alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkylamidopropyl hydroxysultaines, acyl taurates, and acyl glutamates,wherein the alkyl and acyl groups have from 8 to 18 carbon atoms.Non-limiting examples of preferred amphoteric surfactants includecocamidopropyl betaine, sodium cocoamphoacetate, cocamidopropylhydroxysultaine, and sodium cocoamphopropionate, which are particularlysuitable as mild-type cleansers for skin and hair.

Exemplary emulsifiers include but are not limited to C₁₂-C₁₈ fattyalcohols; alkoxylated C₁₂-C₁₈ fatty alcohols; C₁₂-C₁₈ fatty acids; andalkoxylated C₁₂-C₁₈ fatty acids, the alkoxylates each having 10 to 30units of ethylene oxide, propylene oxide, and combinations of ethyleneoxide/propylene oxide; C₈-C₂₂ alkyl mono- and oligoglycosides;ethoxylated sterols; partial esters of polyglycerols; esters and partialesters of polyols having 2 to 6 carbon atoms and saturated andunsaturated fatty acids having 12 to 30 carbon atoms; partial esters ofpolyglycerols; and organosiloxanes; and combinations thereof.

The fatty alcohols, acids and alkoxylated fatty alcohols and fatty acidsare as described in the emollient description above. In one aspect ofthe invention the fatty alcohols and fatty acids each are ethoxylatedwith 10 to 30 units of ethylene oxide.

The C₈-C₂₂ alkyl mono- and oligoglycoside emulsifiers are prepared byreacting glucose or an oligosaccharide with primary fatty alcoholshaving 8 to 22 carbon atoms. Products which are obtainable under thetrademark Plantacare® comprise a glucosidically bonded C₈-C₁₆ alkylgroup on an oligoglucoside residue whose average degree ofoligomerization is 1 to 2. Exemplary alkyl glucosides andoligoglycosides are selected from octyl glucoside, decyl glucoside,lauryl glucoside, palmityl glucoside, isostearyl glucoside, stearylglucoside, arachidyl glucoside and behenyl glucoside, and mixturesthereof.

Exemplary ethoxylated sterols include ethoxylated vegetable oil sterolssuch as, for example, soya sterols. The degree of ethoxylation isgreater than about 5 in one aspect, and at least about 10 in anotheraspect. Suitable ethoxylated sterols are PEG-10 Soy Sterol, PEG-16 SoySterol and PEG-25 Soy Sterol.

The partial esters of polyglycerols have 2 to 10 glycerol units and areesterified with 1 to 4 saturated or unsaturated, linear or branched,optionally hydroxylated C₈-C₃₀ fatty acid residues. Representativepartial esters of polyglycerols include diglycerol monocaprylate,diglycerol monocaprate, diglycerol monolaurate, triglycerolmonocaprylate, triglycerol monocaprate, triglycerol monolaurate,tetraglycerol monocaprylate, tetraglycerol monocaprate, tetraglycerolmonolaurate, pentaglycerol monocaprylate, pentaglycerol monocaprate,pentaglycerol monolaurate, hexaglycerol monocaprylate, hexaglycerolmonocaprate, hexaglycerol monolaurate, hexaglycerol monomyristate,hexaglycerol monostearate, decaglycerol monocaprylate, decaglycerolmonocaprate, decaglycerol monolaurate, decaglycerol monomyristate,decaglycerol monoisostearate, decaglycerol monostearate, decaglycerolmonooleate, decaglycerol monohydroxystearate, decaglycerol dicaprylate,decaglycerol dicaprate, decaglycerol dilaurate, decaglyceroldimyristate, decaglycerol diisostearate, decaglycerol distearate,decaglycerol dioleate, decaglycerol dihydroxystearate, decaglyceroltricaprylate, decaglycerol tricaprate, decaglycerol trilaurate,decaglycerol trimyristate, decaglycerol triisostearate, decaglyceroltristearate, decaglycerol trioleate, decaglycerol trihydroxystearate,and mixtures thereof.

The saturated C₁₂-C₃₀ fatty alcohol emulsifiers are as described in theemollient description set forth above. In one aspect of the invention,the fatty alcohol emulsifier is selected from but not limited to cetylalcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and lanolinalcohol or mixtures of these alcohols, and as are obtainable in thehydrogenation of unsaturated vegetable oil and animal fatty acids.

Emulsifiers based on the esters and partial esters of polyols having 2to 6 carbon atoms and linear saturated and unsaturated fatty acidshaving 12 to 30 carbon atoms are, for example, the monoesters anddiesters of glycerol or ethylene glycol or the monoesters of propyleneglycol with saturated and unsaturated C₁₂-C₃₀ fatty acids.

The partially esterified polyglycerol emulsifiers include 2 to about 10glycerol units and esterified with 1 to 5 saturated or unsaturated,linear or branched, optionally hydroxylated C₈-C₃₀ fatty acid residues.

In one aspect of the invention, the emulsifier can be present in anamount ranging from about 0.5 wt. % to about 12 wt. %, from about 1 wt.% to about 15 wt. % in another aspect, and from about 5 wt. % to about10 wt. % in a further aspect, based on the total weight of the personalcare, home care, health care, and institutional care composition inwhich they are included.

Suitable emollients include but are not limited to an emollient selectedfrom silicone fluids (e.g., volatile silicone oils and non-volatilesilicone oils described below); mineral oils; petrolatums; vegetableoils; fish oils; fatty alcohols; fatty acids; fatty acid and fattyalcohol esters; alkoxylated fatty alcohols; alkoxylated fatty acidesters; benzoate esters; Guerbet esters; alkyl ether derivatives ofpolyethylene glycols, such as, for example methoxypolyethylene glycol(MPEG); and polyalkylene glycols; lanolin and lanolin derivatives; andthe like.

Mineral oils and petrolatums include cosmetic, USP and NF grades and arecommercially available from Penreco under the Drakeol® and Penreco®trade names. Mineral oil includes hexadecane and paraffin oil.

Suitable fatty alcohol emollients include but are not limited to fattyalcohols containing 8 to 30 carbon atoms. Exemplary fatty alcoholsinclude capryl alcohol, pelargonic alcohol, capric alcohol, laurylalcohol, myristyl alcohol, cetyl alcohol, isocetyl alcohol, stearylalcohol, isostearyl alcohol, cetearyl alcohol, oleyl alcohol, ricinoleylalcohol, arachidyl alcohol, icocenyl alcohol, behenyl alcohol, andmixtures thereof.

Suitable fatty acid emollients include but are not limited to fattyacids containing 10 to 30 carbon atoms. Exemplary fatty acids areselected from capric acid, lauric acid, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid,and mixtures thereof.

Exemplary of the fatty acid and fatty alcohol ester emollients includebut are not limited to hexyl laurate, decyl oleate, isopropyl stearate,isopropyl isostearate, butyl stearate, octyl stearate, cetyl stearate,myristyl myristate, octyldodecyl stearoylstearate, octylhydroxystearate,diisopropyl adipate, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, isodecyl oleate, isodecyl neopentanoate, diisopropylsebacate, isostearyl lactate, lauryl lactate, diethyl hexyl maleate,PPG-14 butyl ether and PPG-2 myristyl ether propionate, cetearyloctanoate, and mixtures thereof.

Alkoxylated fatty alcohol emollients are ethers formed from the reactionof a fatty alcohol with an alkylene oxide, generally ethylene oxide orpropylene oxide. Suitable ethoxylated fatty alcohols are adducts offatty alcohols and polyethylene oxide. In one aspect of the invention,the ethoxylated fatty alcohols can be represented by the formulaR′—(OCH₂CH₂)_(n′)—OH, wherein R′ represents the aliphatic residue of theparent fatty alcohol and n represents the number of molecules ofethylene oxide. In another aspect of the invention, R′ is derived from afatty alcohol containing 8 to 30 carbon atoms. In one aspect, n′ is aninteger ranging from 2 to 50, 3 to 25 in another aspect, and 3 to 10 ina further aspect. In a still further aspect, R′ is derived from a fattyalcohol emollient set forth above. Exemplary ethoxylated fatty alcoholsare but are not limited to capryl alcohol ethoxylate, lauryl alcoholethoxylate, myristyl alcohol ethoxylate, cetyl alcohol ethoxylate,stearyl alcohol ethoxylate, cetearyl alcohol ethoxylate oleyl alcoholethoxylate, and, behenyl alcohol ethoxylate, wherein the number ofethylene oxide units in each of the foregoing ethoxylates can range from2 and above in one aspect, and from 2 to about 150 in another aspect. Itis to be recognized that the propoxylated adducts of the foregoing fattyalcohols and mixed ethoxylated/propoxylated adducts of the foregoingfatty alcohols are also contemplated within the scope of the invention.The ethylene oxide and propylene oxide units of theethoxylated/propoxylated fatty alcohols can be arranged in random or inblocky order.

More specific examples of ethoxylated alcohols are but are not limitedto Beheneth 5-30 (the 5-30 meaning the range of repeating ethylene oxideunits), Ceteareth 2-100, Ceteth 1-45, Cetoleth 24-25, Choleth 10-24,Coceth 3-10, C9-11 pareth 3-8, C11-15 pareth 5-40, C11-21 Pareth 3-10,C12-13 pareth 3-15, Deceth 4-6, Dodoxynol 5-12, Glycereth 7-26,Isoceteth 10-30, Isodeceth 4-6, Isolaureth 3-6, isosteareth 3-50, Laneth5-75, Laureth 1-40, Nonoxynol 1-120, Nonylnonoxynol 5-150, Octoxynol3-70, Oleth 2-50, PEG 4-350, Steareth 2-100, and Trideceth 2-10.

Specific examples of propoxylated alcohols are but are not limited toPPG-10 Cetyl Ether, PPG-20 Cetyl Ether, PPG-28 Cetyl Ether, PPG-30 CetylEther, PPG-50 Cetyl Ether, PPG-2 Lanolin Alcohol Ether, PPG-5 LanolinAlcohol Ether, PPG-10 Lanolin Alcohol Ether, PPG-20 Lanolin AlcoholEther, PPG-30 Lanolin Alcohol Ether, PPG-4 Lauryl Ether, PPG-7 LaurylEther, PPG-10 Oleyl Ether, PPG-20 Oleyl Ether, PPG-23 Oleyl Ether,PPG-30 Oleyl Ether, PPG-37 Oleyl Ether, PPG-50 Oleyl Ether, PPG-11Stearyl Ether, PPG-15 Stearyl Ether, PPG-2 Lanolin Ether, PPG-5 LanolinEther, PPG-10 Lanolin Ether, PPG-20 Lanolin Ether, PPG-30 Lanolin Ether,and PPG-1 Myristyl Ether.

Specific examples of ethoxylated/propoxylated alcohols are but are notlimited to PPG-1 Beheneth-15, PPG-12 Capryleth-18, PPG-2-Ceteareth-9,PPG-4-Ceteareth-12, PPG-10-Ceteareth-20, PPG-1-Ceteth-1, PPG-1-Ceteth-5,PPG-1-Ceteth-10, PPG-1-Ceteth-20, PPG-2-Ceteth-1, PPG-2-Ceteth-5,PPG-2-Ceteth-10, PPG-2-Ceteth-20, PPG-4-Ceteth-1, PPG-4-Ceteth-5,PPG-4-Ceteth-10, PPG-4-Ceteth-20, PPG-5-Ceteth-20, PPG-8-Ceteth-1,PPG-8-Ceteth-2, PPG-8-Ceteth-5, PPG-8-Ceteth-10, PPG-8-Ceteth-20, PPG-2C12-13 Pareth-8, PPG-2 C12-15 Pareth-6, PPG-4 C13-15 Pareth-15, PPG-5C9-15 Pareth-6, PPG-6 C9-11 Pareth-5, PPG-6 C12-15 Pareth-12, PPG-6C12-18 Pareth-11, PPG-3 C12-14 Sec-Pareth-7, PPG-4 C12-14 Sec-Pareth-5,PPG-5 C12-14 Sec-Pareth-7, PPG-5 C12-14 Sec-Pareth-9, PPG-1-Deceth-6,PPG-2-Deceth-3, PPG-2-Deceth-5, PPG-2-Deceth-7, PPG-2-Deceth-10,PPG-2-Deceth-12, PPG-2-Deceth-15, PPG-2-Deceth-20, PPG-2-Deceth-30,PPG-2-Deceth-40, PPG-2-Deceth-50, PPG-2-Deceth-60, PPG-4-Deceth-4,PPG-4-Deceth-6, PPG-6-Deceth-4, PPG-6-Deceth-9, PPG-8-Deceth-6,PPG-14-Deceth-6, PPG-6-Decyltetradeceth-12, PPG-6-Decyltetradeceth-20,PPG-6-Decyltetradeceth-30, PPG-13-Decyltetradeceth-24,PPG-20-Decyltetradeceth-10, PPG-2-Isodeceth-4, PPG-2-Isodeceth-6,PPG-2-Isodeceth-8, PPG-2-Isodeceth-9, PPG-2-Isodeceth-10,PPG-2-Isodeceth-12, PPG-2-Isodeceth-18, PPG-2-Isodeceth-25,PPG-4-Isodeceth-10, PPG-12-Laneth-50, PPG-2-Laureth-5, PPG-2-Laureth-8,PPG-2-Laureth-12, PPG-3-Laureth-8, PPG-3-Laureth-9, PPG-3-Laureth-10,PPG-3-Laureth-12, PPG-4 Laureth-2, PPG-4 Laureth-5, PPG-4 Laureth-7,PPG-4-Laureth-15, PPG-5-Laureth-5, PPG-6-Laureth-3, PPG-25-Laureth-25,PPG-7 Lauryl Ether, PPG-3-Myreth-3, PPG-3-Myreth-11, PPG-20-PEG-20Hydrogenated Lanolin, PPG-2-PEG-11 Hydrogenated Lauryl Alcohol Ether,PPG-12-PEG-50 Lanolin, PPG-12-PEG-65 Lanolin Oil, PPG-40-PEG-60 LanolinOil, PPG-1-PEG-9 Lauryl Glycol Ether, PPG-3-PEG-6 Oleyl Ether,PPG-23-Steareth-34, PPG-30 Steareth-4, PPG-34-Steareth-3, PPG-38Steareth-6, PPG-1 Trideceth-6, PPG-4 Trideceth-6, and PPG-6 Trideceth-8.

Alkoxylated fatty acid emollients are formed when a fatty acid isreacted with an alkylene oxide or with a pre-formed polymeric ether. Theresulting product may be a monoester, diester, or mixture thereof.Suitable ethoxylated fatty acid ester emollients suitable for use in thepresent invention are products of the addition of ethylene oxide tofatty acids. The product is a polyethylene oxide ester of a fatty acid.In one aspect of the invention, the ethoxylated fatty acid esters can berepresented by the formula R″—C(O)O(CH₂CH₂O)_(n″)—H, wherein R″represents the aliphatic residue of a fatty acid and n represents thenumber of molecules of ethylene oxide. In another aspect, n″ is aninteger ranging from 2 to 50, 3 to 25 in another aspect, and 3 to 10 ina further aspect. In still another aspect of the invention, R″ isderived from a fatty acid containing 8 to 24 carbon atoms. In a stillfurther aspect, R″ is derived from a fatty acid emollient set forthabove. It is to be recognized that propoxylated andethoxylated/propoxylated products of the foregoing fatty acids are alsocontemplated within the scope of the invention. Exemplary alkoxylatedfatty acid esters include but are not limited to capric acid ethoxylate,lauric acid ethoxylate, myristic acid ethoxylate, stearic acidethoxylate, oleic acid ethoxylate, coconut fatty acid ethoxylate, andpolyethylene glycol 400 propoxylated monolaurate, wherein the number ofethylene oxide units in each of the foregoing ethoxylates can range from2 and above in one aspect, and from 2 to about 50 in another aspect.More specific examples of ethoxylated fatty acids are PEG-8 distearate(the 8 meaning the number of repeating ethylene oxide units), PEG-8behenate, PEG-8 caprate, PEG-8 caprylate, PEG-8 caprylate/caprate, PEGcocoates (PEG without a number designation meaning that the number ofethylene oxide units ranges from 2 to 50), PEG-15 dicocoate, PEG-2diisononanoate, PEG-8 diisostearate, PEG-dilaurates, PEG-dioleatesPEG-distearates, PEG Ditallates, PEG-isostearates, PEG-jojoba acids,PEG-laurates, PEG-linolenates, PEG-myristates, PEG-oleates,PEG-palmitates, PEG-ricinoleates, PEG-stearates, PEG-tallates, and thelike.

Guerbet ester emollients are formed from the esterification reaction ofa Guerbet alcohol with a carboxylic acid. Guerbet ester emollients arecommercially available from the Noveon Consumer Specialties Division ofLubrizol Advanced Materials, Inc. under product designations G-20, G-36,G-38, and G-66.

Lanolin and lanolin derivatives are selected from lanolin, lanolin wax,lanolin oil, lanolin alcohols, lanolin fatty acids, alkoxylated lanolin,isopropyl lanolate, acetylated lanolin alcohols, and combinationsthereof. Lanolin and lanolin derivatives are commercially available fromthe Noveon Consumer Specialties Division of Lubrizol Advanced Materials,Inc. under the trade names Lanolin LP 108 USP, Lanolin USP AAA,Acetulan™, Ceralan™, Lanocerin™, Lanogel™ (product designations 21 and41), Lanogene™, Modulan™, Ohlan™, Solulan™ (product designations 16, 75,L-575, 98, and C-24), Vilvanolin™ (product designations C, CAB, L-101,and P).

The emollient(s) can be utilized in an amount ranging from about 0.5 wt.% to about 30 wt. % by weight of the total personal care composition inone aspect 0.1 wt. % to 25 wt. % in another aspect, and 5 wt. % to 20wt. % in a further aspect. While emollients are generally employed inpersonal care compositions, they can be employed in home care, healthcare, and institutional care compositions in the same wt. ratios as setforth for personal care compositions so long as they effect a desiredphysical attribute (e.g., humectant properties) in such compositions.

Suitable humectants include allantoin, pyrrolidonecarboxylic acid andits salts, hyaluronic acid and its salts, sorbic acid and its salts,urea, lysine, arginine, cystine, guanidine, and other amino acids,polyhydroxy alcohols such as glycerin, propylene glycol, hexyleneglycol, hexanetriol, ethoxydiglycol, dimethicone copolyol, and sorbitol,and the esters thereof, polyethylene glycol, glycolic acid and glycolatesalts (e.g. ammonium and quaternary alkyl ammonium), lactic acid andlactate salts (e.g. ammonium and quaternary alkyl ammonium), sugars andstarches, sugar and starch derivatives (e.g. alkoxylated glucose),panthenols such as dl-panthenol, lactamide monoethanolamine, acetamidemonoethanolamine, and the like, and mixtures thereof. In one embodiment,the humectants include the C₃-C₆ diols and triols, such as glycerin,propylene glycol, hexylene glycol, hexanetriol, and the like, andmixtures thereof. Such suitable humectants typically comprise about 1wt. % to about 10 wt. %, preferably about 2 wt. % to about 8 wt. %, andmore preferably about 3 wt. % to about 5 wt. % of the total weight ofthe personal care compositions of the present invention.

A pH adjusting agent or neutralizer can be added to a formulationcontaining the cationically and hydrophilically modified Cassia polymersof the invention. Thus, the pH adjusting agent can be utilized in anyamount necessary to obtain a desired pH value in the final composition.Non-limiting examples of alkaline pH adjusting agents include alkalimetal hydroxides, such as sodium hydroxide, and potassium hydroxide;ammonium hydroxide; organic bases, such as triethanolamine,diisopropylamine, dodecylamine, diisopropanolamine, aminomethylpropanol, cocamine, oleamine, morpholine, triamylamine, triethylamine,tromethamine (2-amino-2-hydroxymethyl)-1,3-propanediol), andtetrakis(hydroxypropyl)ethylenediamine; and alkali metal salts ofinorganic acids, such as sodium borate (borax), sodium phosphate, sodiumpyrophosphate, and the like, and mixtures thereof. Acidic pH adjustingagents can be organic acids, including amino acids, and inorganicmineral acids. Non-limiting examples of acidic pH adjusting agentsinclude acetic acid, citric acid, fumaric acid, glutamic acid, glycolicacid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid,sodium bisulfate, sulfuric acid, tartaric acid, and the like, andmixtures thereof.

Suitable buffering agents include but are not limited to alkali oralkali earth carbonates, phosphates, bicarbonates, citrates, borates,acetates, acid anhydrides, succinates and the like, such as sodiumphosphate, citrate, borate, acetate, bicarbonate, and carbonate.

The pH adjusting agent and/or buffering agent is utilized in any amountnecessary to obtain and/or maintain a desired pH value in thecomposition. In one aspect, the composition of the invention can containat least one alkalizing (alkaline pH adjusting agent) or acidifyingagent (acidic pH adjusting agent) in amounts from 0.01 to 30 wt. % ofthe total weight of the composition.

The cationically and hydrophilically modified Cassia polymers of thepresent invention can be used as a thickener, film former, anddeposition aid for promoting the deposition of colorants on hair andskin. Colorants for hair can be temporary, semipermanent or permanenthair dyes or color restorers that pigment the hair gradually. Temporaryand semipermanent hair dyes typically are rinses, gels, sprays,shampoos, sticks, and the like, and hair color restorers are typicallyin the form of hair dressings or emulsions. Permanent hair dyes, andlonger-lasting semipermanent hair dyes, are generally two-part products,one part containing the oxidative dye intermediates and dye couplers,and the other part containing stabilized oxidizing agent, usuallyhydrogen peroxide at about pH 3-4, and are mixed together immediatelybefore use. It is known that such two-part hair dyeing products areformulated with combinations of surfactant ingredients, usually nonionicsurfactants or anionic surfactants, to thicken when the dye mixture isprepared. In addition to the foregoing literature, a general discussionof hair dyeing chemistry and compositions is in Brown et al., SCCMonograph, “Permanent Hair Dyes”, Society of Cosmetic Chemists (1996),incorporated herein by reference. The polymers of the present inventionmay be incorporated in one or both of the two-parts of such hair dyeingsystems, either as the thickener for the acidic stabilized oxidizingportion or in the non-oxidizing portion to be thickened upon mixing withthe acidic portion.

In addition to ingredients discussed above, other ingredients commonlyused for antiacne products, facial and body hair bleaches, andantiseptic products include oxidizing agents, such as hydrogen peroxide,benzoyl peroxide, and water-soluble inorganic persulfate compounds suchas ammonium persulfate, potassium persulfate, and sodium persulfate.

The cationically and hydrophilically modified Cassia polymers of thepresent invention are surprisingly useful stabilizers and/or depositionaids for silicone conditioning agents which are commonly used in rinseoff hair conditioner products and in shampoo products, such as theso-called “two-in-one” combination cleansing/conditioning shampoos. Theconditioning agent is preferably an insoluble silicone conditioningagent. Typically, the conditioning agent will be mixed in the shampoocomposition to form a separate, discontinuous phase of dispersed,insoluble particles (also referred to as droplets). The silicone hairconditioning agent phase can be a silicone fluid and can also compriseother ingredients, such as a silicone resin, to improve silicone fluiddeposition efficiency or enhance the glossiness of the hair especiallywhen high refractive index (e.g., above about 1.46) siliconeconditioning agents are used. The optional silicone hair conditioningagent phase may comprise volatile silicone, nonvolatile silicone, orcombinations thereof. The silicone droplets are typically suspended withan optional suspending agent. The silicone conditioning agent particlesmay comprise volatile silicone, non-volatile silicone, or combinationsthereof. Preferred are non-volatile silicone conditioning agents. Ifvolatile silicones are present, they will typically be incidental totheir use as a solvent or carrier for commercially available forms ofnon-volatile silicone materials ingredients, such as silicone gums andresins. The silicone hair conditioning agents for use in the presentinvention have a viscosity of from about 20 to about 2,000,000centistokes (1 centistokes equals 1×10⁻⁶ m²/s) in one aspect, from about1,000 to about 1,800,000 centistokes in another aspect, from about50,000 to about 1,500,000 in a further aspect, and from about 100,000 toabout 1,500,000 centistokes in a still further aspect, as measured at25° C.

The concentration of the silicone conditioning agent can range fromabout 0.01% to about 10%, by weight of the composition in which it isincluded. In another aspect, the amount of silicone conditioning agentranges from about 0.1% to about 8%, from about 0.1% to about 5% in stillanother aspect, and from about 0.2% to about 3% by wt. in a furtheraspect, all based on the total weight of the composition.

In one embodiment, the dispersed silicone conditioning agent particlescan have a volume average particle diameter ranging from about 5 μm toabout 125 μm. For small particle application to hair, the volume averageparticle diameters range from about 0.01 μm to about 4 μmin one aspect,from about 0.01 μm to about 2 μm in another aspect, and from about 0.01μm to about 0.5 μm in still another aspect. For larger particleapplication to hair, the volume average particle diameters typicallyrange from about 5 μm to about 125 μm in one aspect, from about 10 μm toabout 90 μm in another aspect, from about 15 μm to about 70 μm in stillanother aspect, and from about 20 μm to about 50 μm in a further aspect.

Background material on silicones including sections discussing siliconefluids, gums, and resins, as well as manufacture of silicones, are foundin Encyclopedia of Polymer Science and Engineering, vol. 15, 2d ed., pp204-308, John Wiley & Sons, Inc. (1989), incorporated herein byreference. Silicone fluids are generally described as alkylsiloxanepolymers. Non-limiting examples of suitable silicone conditioningagents, and optional suspending agents for the silicone, are describedin U.S. Reissue Pat. No. 34,584, U.S. Pat. No. 5,104,646, and U.S. Pat.No. 5,106,609, which descriptions are incorporated herein by reference.

Silicone fluids include silicone oils, which are flowable siliconematerials having a viscosity, as measured at 25° C. of less than1,000,000 cSt, and typically range from about 5 cSt to about 1,000,000cSt. Suitable silicone oils include polyalkyl siloxanes, polyarylsiloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers, andmixtures thereof. Other insoluble, non-volatile silicone fluids havinghair conditioning properties may also be used.

Silicone oils include polyalkyl, polyaryl siloxanes, or polyalkylarylsiloxanes which conform to the following formula:

wherein R²⁰ is aliphatic, independently selected from alkyl, alkenyl,and aryl, R²⁰ can be substituted or unsubstituted, and w is an integerfrom 1 to about 8,000. Suitable unsubstituted R²⁰ groups for use in thepersonal cleansing compositions of the present invention include, butare not limited to: alkoxy, aryloxy, alkaryl, arylalkyl, arylalkenyl,alkamino, and ether-substituted, hydroxyl-substituted, andhalogen-substituted aliphatic and aryl groups. Suitable R²⁰ groups alsoinclude cationic amines and quaternary ammonium groups.

In one aspect of the invention, exemplary R²⁰ alkyl and alkenylsubstituents range from C₁-C₅ alkyl and alkenyl, from C₁-C₄ in anotheraspect, from C₁-C₂ in a further aspect. The aliphatic portions of otheralkyl-, alkenyl-, or alkynyl-containing groups (such as alkoxy, alkaryl,and alkamino) can be straight or branched chains, and range from C₁-C₅in one aspect, from C₁-C₄ in another aspect, and from C₁-C₂ in a furtheraspect. As discussed above, the R²⁰ substituents can also contain aminofunctionalities (e.g. alkamino groups), which can be primary, secondaryor tertiary amines or quaternary ammonium. These include mono-, di- andtri-alkylamino and alkoxyamino groups, wherein the aliphatic portionchain length is as described above.

Exemplary siloxanes are polydimethyl siloxane, polydiethylsiloxane, andpolymethylphenylsiloxane. These siloxanes are available, for example,from the General Electric Company in their Viscasil R and SF 96 series,and from Dow Corning marketed under the Dow Corning 200 series.Exemplary polyalkylaryl siloxane fluids that may be used, include, forexample, polymethylphenylsiloxanes. These siloxanes are available, forexample, from the General Electric Company as SF 1075 methyl phenylfluid or from Dow Corning as 556 Cosmetic Grade Fluid.

Cationic silicone fluids are also suitable for use with the cationicallyand hydrophilically modified Cassia polymers of the invention. Thecationic silicone fluids can be represented, but are not limited, to thegeneral formula):

(R²¹)_(e)G_(3-f)-Si—(OSiG₂)_(g)-(OSiG_(f)(R₁)_((2-f)h)—O—SiG_(3-e)(R²¹)_(f)

wherein G is hydrogen, phenyl, hydroxy, or C₁-C₈ alkyl, preferablymethyl; e is 0 or an integer having of from 1 to 3; f is 0 or 1; g is anumber from 0 to 1,999; h is an integer from 1 to 2,000, preferably from1 to 10; the sum of g and h is a number from 1 to 2,000 in one aspect,and from 50 to 500 in another aspect of the invention; R²¹ is amonovalent radical conforming to the general formula C_(q)H_(2q)L,wherein q is an integer having a value from 2 to 8 and L is selectedfrom the following groups:

a) —N(R²²)CH₂CH₂N(R²²)₂

b) —N(R²²)

c) —N(R²²)₃CA⁻

d) —N(R²²)CH₂CH₂N(R²²)₂H₂CA⁻

wherein R²² is independently selected from hydrogen, C₁-C₂₀ alkyl,phenyl, benzyl; and A⁻ is a halide ion selected from chloride, bromide,fluoride, and iodide.

An exemplary cationic silicone corresponding to the previous formuladefined immediately above is the polymer known as“trimethylsilylamodimethicone” of formula:

(CH₃)₃—Si-[O—Si(CH₃)₂)]_(g)—[O—(CH₃)Si((CH₂)₃—NH—(CH₂)₂—NH₂)]_(h)—O—Si(CH₃)₃

Another cationic silicone useful in combination with the cationicallyand hydrophilically modified Cassia polymers of the invention can berepresented by the formula:

wherein where R²² represents a radical selected from a C₁-C₁₈ alkyl andC₁-C₁₈ alkenyl radical; R²³ independently represents a radical selectedfrom a C₁-C₁₈ alkylene radical or a C₁-C₁₈ alkyleneoxy radical; Q is ahalide ion; r denotes an average statistical value from 2 to 20 in oneaspect, and from 2 to 8 in another aspect; s denotes an averagestatistical value from 20 to 200 in one aspect, and from 20 to 50 inanother aspect. In one aspect, R²² is methyl. In another aspect, Q ischloride.

Other optional silicone fluids are the insoluble silicone gums. Thesegums are polysiloxane materials having a viscosity at 25° C. of greaterthan or equal to 1,000,000 centistokes. Silicone gums are described inU.S. Pat. No. 4,152,416; Noll and Walter, Chemistry and Technology ofSilicones, New York: Academic Press 1968; and in General ElectricSilicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76, allof which are incorporated herein by reference. The silicone gums willtypically have a mass molecule weight in excess of about 200,000Daltons, generally between about 200,000 to about 1,000,000 Daltons,specific examples of which include polydimethylsiloxane,polydimethylsiloxane/methylvinylsiloxane copolymer,polydimethylsiloxane/diphenyl siloxane/methylvinylsiloxane) copolymer,and mixtures thereof.

Another category of nonvolatile, insoluble silicone fluid conditioningagents are the high refractive index polysiloxanes, having a refractiveindex of at least about 1.46 in one aspect, at least about 1.48 inanother aspect, at least about 1.52 in a further aspect, and at leastabout 1.55 in a still further aspect. The refractive index of thepolysiloxane fluid will generally be less than about 1.70, typicallyless than about 1.60. In this context, polysiloxane “fluid” includesoils as well as gums.

The high refractive index polysiloxane fluid includes those representedby the general formula set forth for the polyalkyl, polyaryl, andpolyalkylaryl siloxanes described above, as well as cyclic polysiloxanes(cyclomethicones) represented by the

wherein the substituent R²⁰ is as defined above, and the number ofrepeat units, k, ranges from about 3 to about 7 in one aspect, and from3 to 5 in another aspect. The high refractive index polysiloxane fluidscan contain an amount of aryl containing R²⁰ substituents sufficient toincrease the refractive index to the desired level, which is describedabove. Additionally, R²⁰ and k must be selected so that the material isnon-volatile. Aryl containing substituents include those which containalicyclic and heterocyclic five and six member aryl rings and thosewhich contain fused five or six member rings. The aryl rings can besubstituted or unsubstituted. Substituents include aliphaticsubstituents, and can also include alkoxy substituents, acylsubstituents, ketones, halogens (e.g., Cl and Br), amines, etc.Exemplary aryl containing groups include substituted and unsubstitutedarenes, such as phenyl, and phenyl derivatives such as phenyls withC₁-C₅ alkyl or alkenyl substituents, e.g., allylphenyl, methyl phenyland ethyl phenyl, vinyl phenyls such as styrenyl, and phenyl alkynes(e.g. phenyl C₂-C₄ alkynes). Heterocyclic aryl groups includesubstituents derived from furan, imidazole, pyrrole, pyridine, etc.Fused aryl ring substituents include, for example, naphthalene,coumarin, and purine.

The high refractive index polysiloxane fluids will have a degree of arylcontaining substituents of at least about 15% by wt. in one aspect, atleast about 20% by wt. in another aspect, at least about 25% by wt. in afurther aspect, at least about 35% by wt. in still further aspect, andat least about 50% by wt. in an additional aspect, based on the wt. ofthe polysiloxane fluid. Typically, the degree of aryl substitution willbe less than about 90% by wt., more typically less than about 85% bywt., and can generally ranges from about 55% to about 80% by wt. of thepolysiloxane fluid.

In another aspect, the high refractive index polysiloxane fluids have acombination of phenyl or substituted phenyl derivatives. Thesubstituents can be selected from C₁-C₄ alkyl (e.g., methyl), hydroxy,and C₁-C₄ alkylamino (e.g., —R²⁴NHR²⁵NH₂ wherein each R²⁴ and R²⁵ groupindependently is a C₁-C₃ alkyl, alkenyl, and/or alkoxy.

When high refractive index silicones are used in the compositions of thepresent invention, they optionally can be used in solution with aspreading agent, such as a silicone resin or a surfactant, to reduce thesurface tension by a sufficient amount to enhance spreading and therebyenhance the glossiness (subsequent to drying) of hair treated with suchcompositions. Silicone fluids suitable for use in the compositions ofthe present invention are disclosed in U.S. Pat. No. 2,826,551, U.S.Pat. No. 3,964,500, U.S. Pat. No. 4,364,837, British Pat. No. 849,433,and Silicon Compounds, Petrarch Systems, Inc. (1984), all of which areincorporated herein by reference. High refractive index polysiloxanesare available from Dow Corning Corporation (Midland, Mich.) Huls America(Piscataway, N.J.), and General Electric Silicones (Waterford, N.Y.).

Silicone resins can be included in the silicone conditioning agentsuitable for use in combination with the cationically andhydrophilically modified Cassia polymers of the present invention. Theseresins are crosslinked polysiloxanes. The crosslinking is introducedthrough the incorporation of trifunctional and tetrafunctional silaneswith monofunctional or difunctional (or both) silanes during manufactureof the silicone resin.

As is well understood in the art, the degree of crosslinking that isrequired in order to result in a silicone resin will vary according tothe specific silane units incorporated into the silicone resin. Ingeneral, silicone materials which have a sufficient level oftrifunctional and tetrafunctional siloxane monomer units (and hence, asufficient level of crosslinking) such that they dry down to a rigid, orhard, film are considered to be silicone resins. The ratio of oxygenatoms to silicon atoms is indicative of the level of crosslinking in aparticular silicone material. Silicone materials which have at leastabout 1.1 oxygen atoms per silicon atom will generally be siliconeresins herein. In one aspect, the ratio of oxygen:silicon atoms is atleast about 1.2:1.0. Silanes used in the manufacture of silicone resinsinclude monomethyl-, dimethyl-, trimethyl-, monophenyl-, diphenyl-,methylphenyl-, monovinyl-, and methylvinyl-chlorosilanes, andterachlorosilane, with the methyl-substituted silanes being mostcommonly utilized. Silicone resins are offered by General Electric as GESS4230 and SS4267.

Silicone materials and silicone resins in particular, are identifiedaccording to a shorthand nomenclature system known to those of ordinaryskill in the art as “MDTQ” nomenclature. Under this system, the siliconeis described according to the presence of various siloxane monomer unitswhich make up the silicone. Briefly, the symbol M denotes themonofunctional unit (CH₃)₃SiO_(0.5); D denotes the difunctional unit(CH₃)₂SiO; T denotes the trifunctional unit (CH₃)SiO_(1.5); and Qdenotes the quadra- or tetra-functional unit SiO₂. Primes of the unitsymbols (e.g. M′, D′, T′, and Q′) denote substituents other than methyl,and must be specifically defined for each occurrence. Typical alternatesubstituents include groups such as vinyl, phenyls, amines, hydroxyls,etc. The molar ratios of the various units, either in terms ofsubscripts to the symbol indicating the total number of each type ofunit in the silicone (or an average thereof) or as specificallyindicated ratios in combination with molecular weight complete thedescription of the silicone material under the MDTQ system. Higherrelative molar amounts of T, Q, T′ and/or Q′ to D, D′, M and/or M′ in asilicone resin is indicative of higher levels of crosslinking. Asdiscussed before, however, the overall level of crosslinking can also beindicated by the oxygen to silicon ratio.

Exemplary silicone resins for use in the compositions of the presentinvention include, but are not limited to MQ, MT, MTQ, MDT and MDTQresins. In one aspect, methyl is the silicone resin substituent. Inanother aspect, the silicone resin is selected from a MQ resins, whereinthe M:Q ratio is from about 0.5:1.0 to about 1.5:1.0 and the averagemolecular weight of the silicone resin is from about 1000 to about10,000 Daltons.

When employed with non-volatile silicone fluids having a refractiveindex below 1.46, the weight ratio of the non-volatile silicone fluid tothe silicone resin component, ranges from about 4:1 to about 400:1 inone aspect, from about 9:1 to about 200:1 in another aspect, from about19:1 to about 100:1 in a further aspect, particularly when the siliconefluid component is a polydimethylsiloxane fluid or a mixture ofpolydimethylsiloxane fluid and polydimethylsiloxane gum as describedabove. Insofar as the silicone resin forms a part of the same phase inthe compositions hereof as the silicone fluid, i.e., the conditioningactive, the sum of the fluid and resin should be included in determiningthe level of silicone conditioning agent in the composition.

The volatile silicones described above include cyclic and linearpolydimethylsiloxanes, and the like. Cyclic volatile silicones(cyclomethicones) typically contain about 3 to about 7 silicon atoms,alternating with oxygen atoms, in a cyclic ring structure such asdescribed above for the non-volatile cyclic silicones. However, each R²⁰substituent and repeating unit, k, in the formula must be selected sothat the material is non-volatile. Typically, R²⁰ is substituted withtwo alkyl groups (e.g., methyl groups). The linear volatile siliconesare silicone fluids, as described above, having viscosities of not morethan about 25 mPa·s. “Volatile” means that the silicone has a measurablevapor pressure, or a vapor pressure of at least 2 mm of Hg at 20° C.Non-volatile silicones have a vapor pressure of less than 2 mm Hg at 20°C. A description of cyclic and linear volatile silicones is found inTodd and Byers, “Volatile Silicone Fluids for Cosmetics”, Cosmetics andToiletries, Vol. 91(1), pp. 27-32 (1976), and in Kasprzak, “VolatileSilicones”, Soap/Cosmetics/Chemical Specialities, pp. 40-43 (December1986), each incorporated herein by reference.

Exemplary volatile cyclomethicones are D4 cyclomethicone(octamethylcyclotetrasiloxane), D5 cyclomethicone(decamethylcyclopentasiloxane), D6 cyclomethicone, and blends thereof(e.g., D4/D5 and D5/D6). Volatile cyclomethicones and cyclomethiconeblends are commercially available from G.E. Silicones as SF1173, SF1202,SF1256, and SF1258, Dow Corning Corporation as Dow Corning® 244, 245,246, 345, and 1401 Fluids. Blends of volatile cyclomethicones andvolatile linear dimethicones are also contemplated.

Exemplary volatile linear dimethicones include hexamethyldisiloxane,octamethyltrisiloxane, decamethyltetrasiloxane,dodecamethylpentasiloxane and blends thereof. Volatile lineardimethicones and dimethicone blends are commercially available from DowCorning Corporation as Dow Corning 200® Fluid (e.g., productdesignations 0.65 CST, 1 CST, 1.5 CST, and 2 CST) and Dow Corning®2-1184 Fluid.

Emulsified silicones are also suitable for combination with thecationically and hydrophilically modified Cassia polymers of theinvention. Typically, silicone emulsions have an average siliconeparticle size in the composition of less than 30 μm in one aspect, lessthan 20 μm in another aspect, and less than 10 μm in a further aspect.In one embodiment of the invention, the average silicone particle sizeof the emulsified silicone in the composition is less than 2 μm, andideally it ranges from 0.01 to 1 μm. Silicone emulsions having anaverage silicone particle size of <0.15 micrometers are generally termedmicro-emulsions. Particle size may be measured by means of a laser lightscattering technique, using a 2600D Particle Sizer from MalvernInstruments. Suitable silicone emulsions for use in the invention arealso commercially available in a pre-emulsified form. Examples ofsuitable pre-formed emulsions include emulsions DC2-1766, DC2-1784, andmicro-emulsions DC2-1865 and DC2-1870, all available from Dow Corning.These are all emulsions/micro-emulsions of dimethiconol. Crosslinkedsilicone gums are also available in a pre-emulsified form, which isadvantageous for ease of formulation. An exemplary material is availablefrom Dow Corning as DC X2-1787, which is an emulsion of crosslinkeddimethiconol gum. Another exemplary material is available from DowCorning as DC X2-1391, which is a micro-emulsion of crosslinkeddimethiconol gum. Preformed emulsions of amino functional silicone arealso available from suppliers of silicone oils such as Dow Corning andGeneral Electric. Particularly suitable are emulsions of aminofunctional silicone oils with non ionic and/or cationic surfactant.Specific examples include DC929 Cationic Emulsion, DC939 CationicEmulsion, DC949 Cationic emulsion, and the non-ionic emulsions DC2-7224,DC2-8467, DC2-8177 and DC2-8154 (all available from Dow Corning).Mixtures of any of the above types of silicone may also be used.Specific examples of amino functional silicones suitable are theaminosilicone oils DC2-8220, DC2-8166, DC2-8466, and DC2-8950-114 (allavailable from Dow Corning), and GE 1149-75, (ex General ElectricSilicones). An example of a quaternary silicone polymer useful in thepresent invention is the material K3474, available from Goldschmidt,Germany.

Other suitable silicone oils include the dimethicone copolyols, whichare linear or branched copolymers of dimethylsiloxane (dimethicone)modified with alkylene oxide units. The alkylene oxide units can bearranged as random or block copolymers. A generally useful class ofdimethicone polyols are block copolymers having terminal and/or pendentblocks of polydimethylsiloxane and blocks of polyalkylene oxide, such asblocks of polyethylene oxide, polypropylene oxide, or both. Dimethiconecopolyols can be water soluble or insoluble depending on the amount ofpolyalkylene oxide present in the dimethicone polymer and can beanionic, cationic, or nonionic in character.

The water soluble or water dispersible silicones can also be used incombination with the cationically and hydrophilically modified Cassiapolymers of the invention. Such water soluble silicones contain suitableanionic functionality, cationic functionality, and/or nonionicfunctionality to render the silicone water soluble or water dispersible.In one embodiment, the water soluble silicones contain a polysiloxanemain chain to which is grafted at least one anionic moiety. The anionicmoiety can be grafted to a terminal end of the polysiloxane backbone, orbe grafted as a pendant side group, or both. By anionic group is meantany hydrocarbon moiety that contains at least one anionic group or atleast one group that can be ionized to an anionic group followingneutralization by a base. As discussed previously, the quantity of thehydrocarbon groups of anionic character which are grafted onto thesilicone chain are chosen so that the corresponding silicone derivativeis water-soluble or water-dispersible after neutralization of theionizable groups with a base. The anionic silicone derivatives can beselected from existing commercial products or can be synthesized by anymeans known in the art. The nonionic silicones contain alkylene oxideterminal and/or pendant side chain units (e.g., dimethicone copolyols).

Silicones with anionic groups can be synthesized by reaction between (i)a polysiloxane containing a silinic hydrogen and (ii) a compoundcontaining olefinic unsaturation that also contains an anionicfunctional group. Exemplary of such a reaction is the hydrosilylationreaction between poly(dimethylsiloxanes) containing a Si—H group(s) andan olefin, CH₂═CHR²⁶, wherein R²⁶ represents a moiety containing ananionic group. The olefin can be monomeric, oligomeric or polymeric.Polysiloxane compounds that contain a pendant reactive thio (—SH)group(s) are also suitable for grafting an unsaturated anionic groupcontaining compound to the poly(siloxane) backbone.

According to one aspect of the present invention, the anionic monomerscontaining ethylenic unsaturation are used alone or in combination andare selected from linear or branched, unsaturated carboxylic acids.Exemplary unsaturated carboxylic acids are acrylic acid, methacrylicacid, maleic acid, maleic anhydride, itaconic acid, fumaric acid andcrotonic acid. The monomers can optionally be partially or completelyneutralized by base to form an alkali, alkaline earth metal, andammonium salt. Suitable bases include but are not limited to the alkali,alkaline earth (e.g., sodium, potassium, lithium, calcium) and ammoniumhydroxides. It will be noted that, similarly, the oligomeric andpolymeric graft segments formed from the forgoing monomers can bepost-neutralized with a base (sodium hydroxide, aqueous ammonia, etc.)to form a salt. Examples of silicone derivatives which are suitable foruse in the present invention are described in patent applicationsnumbers EP-A-0 582,152 and WO 93/23009. An exemplary class of siliconepolymers are the polysiloxanes containing repeat units represented bythe following structure:

wherein G¹ represents hydrogen, C₁-C₁₀ alkyl and phenyl radical; G²represents C₁-C₁₀ alkylene; G³ represents an anionic polymeric residueobtained from the polymerization of at least one anionic monomercontaining ethylenic unsaturation; j is 0 or 1; t is an integer rangingfrom 1 to 50; and u is an integer from 10 to 350. In one embodiment ofthe invention, G¹ is methyl; j is 1; and G₂ is propylene radical; G³represents a polymeric radical obtained from the polymerization of atleast one unsaturated monomer containing a carboxylic acid group (e.g.,acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonicacid, maleic acid, or aconitic acid, and the like).

The carboxylate group content in the final polymer preferably rangesfrom 1 mole of carboxylate per 200 g of polymer to 1 mole of carboxylateper 5000 g of polymer. The number molecular mass of the silicone polymerpreferably ranges from 10,000 to 1,000,000 and still more preferablyfrom 10,000 to 100,000. Exemplary unsaturated monomers containingcarboxylic acid groups are acrylic acid and methacrylic acid. Inaddition, to the carboxylic acid group containing monomers, C₁-C₂₀ alkylesters of acrylic acid and methacrylic acid can be copolymerized intothe polymeric backbone. Exemplary esters include but are not limited tothe ethyl and butyl esters of acrylic and methacrylic acid. Acommercially available silicone-acrylate polymer is marketed by the 3MCompany under the trademark Silicones “Plus” Polymer 9857C (VS80 Dry).These polymers contain a polydimethylsiloxanes (PDMS) backbone ontowhich is grafted (through a thiopropylene group) random repeating unitsof poly(meth)acrylic acid and the butyl ester of poly(meth)acrylate.These products can be obtained conventionally by radicalcopolymerization between thiopropyl functionalized polydimethylsiloxaneand a mixture of monomers comprising (meth)acrylic acid and ofbutyl(meth)acrylate.

In another embodiment, the water soluble silicone copolyol useful in thepractice of the present invention can be represented silicone copolyolcarboxylates represented by the formula:

where R²⁷ and R²⁸ are independently selected from C₁-C₃₀ alkyl, C₆-C₁₄aryl, C₇-C₁₅ aralkyl, C₁-C₁₅ alkaryl, or an alkenyl group of 1 to 40carbons, hydroxyl, —R³¹-G′ or —(CH₂)₃O(EO)_(a)(PO)_(b)(EO)_(c)-G′, withthe proviso that both R²⁷ and R²⁸ are not methyl; R²⁹ is selected fromC₁-C₅ alkyl or phenyl; in this formula a, b, and c are integersindependently ranging from 0 to 100; EO is ethylene oxide, —(CH₂CH₂O)—;PO is propylene oxide, —(CH₂CH(CH₃)O)—; in this formula o is an integerranging from 1 to 200, p is an integer ranging from 0 to 200, and q isan integer ranging from 0 to 1000; R³⁰ is hydrogen, C₁-C₃₀ alkyl, aryl,C₇-C₁₅ aralkyl, C₇-C₁₅ alkaryl, or alkenyl group of 1 to 40 carbons or—C(O)—X wherein X is C₁-C₃₀ alkyl, C₆-C₁₄ aryl, C₇-C₁₅ aralkyl,C₁-C₁₅alkaryl, or an alkenyl group of 1 to 40 carbons, or a mixturethereof; R³¹ is a divalent group selected from alkylene radical of 1 to40 carbon atoms which may be interrupted with arylene group of 6 to 18carbons or an alkylene group containing unsaturation of 2 to 8 carbons;and G′ is independently are selected from:

where R³² is a divalent group selected from alkylene of 1 to 40 carbons,an unsaturated group containing 2 to 5 carbon atoms, or an arylene groupof 6 to 12 carbon atoms; where M is a cation selected from Na, K, Li,NH₄, or an amine containing C₁-C₁₀ alkyl, C₆-C₁₄ aryl (e.g., phenyl,naphthyl), C₂-C₁₀ alkenyl, C₁-C₁₀ hydroxyalkyl, C₇-C₂₄ arylalkyl orC₇-C₂₄ alkaryl groups. Representative R³² radicals are: —CH₂CH₂—,—CH═CH—, —CH═CHCH₂—, and phenylene.

In another embodiment, the water soluble silicones useful in thepractice of the present invention can be represented an anionic siliconecopolyol represented by the

where is R³³ is methyl or hydroxyl; R³⁴ is selected from C₁-C₈ alkyl orphenyl; R³⁵ represents the radical —(CH₂)₃O(EO)_(x)(PO)_(y)(EO)_(z)—SO₃⁻M⁺; where M is a cation selected from Na, K, Li, or NH₄; in thisformula x, y and z are integers independently ranging from 0 to 100; R³⁶represents the radical —(CH₂)₃O(EO)_(x)(PO)_(y)(EO)_(z)—H; in thisformula a and c are independently integers ranging from 0 to 50, and bis an integer ranging from 1 to 50; EO is ethylene oxide, e.g.,—(CH₂CH₂O)—; PO is propylene oxide, e.g., —(CH₂CH(CH₃)O)—.

In still another embodiment, the water soluble silicones useful in thepractice of the present invention can be represented an anionic siliconecopolyol represented by the formula:

wherein R³⁷ and R³⁸ independently are —CH₃ or a radical represented by:—(CH₂)₃O(EO)_(a)(PO)_(b)(EO)_(c)—C(O)—R⁴⁰—C(O)OH, subject to the provisothat both R³⁷ and R³⁸ are not —CH₃ at the same time; R⁴⁰ is selectedfrom the divalent radical —CH₂CH₂, —CH═CH—, and phenylene; R³⁹ isselected from C₁-C₅ alkyl or phenyl; in this formula a, b and c areintegers independently ranging from 0 to 20; EO is an ethylene oxideresidue, e.g., —(CH₂CH₂O)—; PO is a propylene oxide residue, e.g.,—(CH₂CH(CH₃)O)—; in this formula o is an integer ranging from 1 to 200and q is an integer ranging from 0 to 500.

Other water soluble silicones useful in the invention are quaternizedsilicone copolyol polymers. These polymers have a pendant quaternarynitrogen functional group present and are represented by the formula:

where R⁴¹ represents a quaternary substituent —N⁺R³R⁴R⁵X⁻, wherein R³and R⁴, and R⁵, independently, are selected from hydrogen and linear andbranched C₁-C₂₄ alkyl, and X⁻ represents an anion suitable to balancethe cationic charge on the nitrogen atom; R⁴² is selected from C₁-C₁₀alkyl and phenyl; R⁴³ is —(CH₂)₃O(EO)_(x)(PO)_(y)(EO)_(z)—H, where EO isan ethylene oxide residue, e.g., —(CH₂CH₂O)—; PO is a propylene oxideresidue, e.g., —(CH₂CH(CH₃)O)—; in this formula a is an integer from 0to 200, b is an integer from 0 to 200, and c is an integer from 1 to200; in this formula x, y and z are integers and are independentlyselected from 0 to 20. In one aspect, the anion X⁻ represents an anionselected from chloride, bromide, iodide, sulfate, methylsulfate,sulfonate, nitrate, phosphate, and acetate.

Other suitable water soluble silicones are amine substituted siliconecopolyols represented by the formula:

where R⁴⁴ is selected from —NH(CH₂)_(n)NH₂ or —(CH₂)_(n)NH₂, where inthis formula n is an integer from 2 to 6; and x, is n integer from 0 to20; where EO is an ethylene oxide residue, e.g., —(CH₂CH₂O)—; PO is apropylene oxide residue, e.g., —(CH₂CH(CH₃)O)—; in this formula a is aninteger from 0 to 200, b is an integer from 0 to 200, and c is aninteger from 1 to 200; in this formula x, y and z are integers and areindependently selected from 0 to 20.

Still other water soluble silicones can be selected from nonionicsilicone copolyols (dimethicone copolyols) represented by the formula:

where R⁴⁵, independently, represents a radical selected from C₁-C₃₀alkyl, C₆-C₁₄ aryl, and C₂-C₂₀ alkenyl; R⁴⁶ represents a radicalselected from C₁-C₃₀ alkyl, C₆-C₁₄ aryl, and C₂-C₂₀ alkenyl; EO is anethylene oxide residue, e.g., —(CH₂CH₂O)—; PO is a propylene oxideresidue, e.g., —(CH₂CH(CH₃)O)—; in this formula a, b, and c are,independently, 0 to 100; in this formula x is 0 to 200; and y is 1 to200.

In another embodiment, water soluble silicones can be selected fromnonionic silicone copolyols represented by the formula:

wherein R⁴⁸ and R⁴⁹, independently, represent a radical selected fromC₁-C₃₀ alkyl, C₆-C₁₄ aryl, and C₂-C₂₀ alkenyl; EO is an ethylene oxideresidue, e.g., —(CH₂CH₂O)—; PO is a propylene oxide residue, e.g.,—(CH₂CH(CH₃)O)—; in this formula a, b, and c are independently 0 to 100;and in this formula n is 0 to 200.

In the copolyol embodiments set forth above, the EO and PO residues canbe arranged in random, non-random, or blocky sequences.

Dimethicone copolyols are disclosed in U.S. Pat. Nos. 5,136,063 and5,180,843, the disclosures of which are incorporated herein byreference. In addition, dimethicone copolyols are commercially availableunder the Silsoft® and Silwet® brand names from the General ElectricCompany (GE-OSi). Specific product designations include but are notlimited to Silsoft 305, 430, 475, 810, 895, Silwet L 7604 (GE-OSi); DowCorning® 5103 and 5329 from Dow Corning Corporation; and Abil®dimethicone copolyols, such as, for example WE 09, WS 08, EM 90 and EM97 from Evonik Goldschmidt Corporation; and Silsense™ dimethiconecopolyols, such as Silsense Copolyol-1 and Silsense Copolyol-7,available from Lubrizol Advanced Materials, Inc.

The conditioning component of the conditioner and shampoo compositionsof the present invention can also comprise from about 0.05% to about 3%,by weight of the composition in one aspect, from about 0.08% to about1.5% in another aspect, and from about 0.1% to about 1% in a furtheraspect, of at least one conditioning oil as the conditioning agent,either alone or in combination with other conditioning agents, such asthe silicones (described above) and the other conditioning agentsdescribed below.

Suitable conditioning oils for use as conditioning agents in thecompositions of the present invention include, but are not limited to,hydrocarbon oils having at least about 10 carbon atoms, such as cyclichydrocarbons, straight chain aliphatic hydrocarbons (saturated orunsaturated), and branched chain aliphatic hydrocarbons (saturated orunsaturated), including polymers and mixtures thereof. Straight chainhydrocarbon oils typically contain about 12 to 19 carbon atoms. Branchedchain hydrocarbon oils, including hydrocarbon polymers, typically willcontain more than 19 carbon atoms.

Specific non-limiting examples of these hydrocarbon oils includeparaffin oil, mineral oil, saturated and unsaturated dodecane, saturatedand unsaturated tridecane, saturated and unsaturated tetradecane,saturated and unsaturated pentadecane, saturated and unsaturatedhexadecane, polybutene, polydecene, and mixtures thereof. Branched-chainisomers of these compounds, as well as of higher chain lengthhydrocarbons, can also be used, examples of which include highlybranched, saturated or unsaturated, alkanes such as thepermethyl-substituted isomers, e.g., the permethyl-substituted isomersof hexadecane and eicosane, such as2,2,4,4,6,6,8,8-dimethyl-10-methylundecane and2,2,4,4,6,6-dimethyl-8-methylnonane, available from PermethylCorporation. Hydrocarbon polymers such as polybutene and polydecene. Apreferred hydrocarbon polymer is polybutene, such as the copolymer ofisobutylene and butene. A commercially available material of this typeis L-14 polybutene from BP Chemical Company.

Natural oil conditioners are also useful in the practice of thisinvention and include but are not limited to peanut, sesame, avocado,coconut, cocoa butter, almond, safflower, corn, cotton seed, sesameseed, walnut oil, castor, olive, jojoba, palm, palm kernel, soybean,wheat germ, linseed, sunflower seed; eucalyptus, lavender, vetiver,litsea, cubeba, lemon, sandalwood, rosemary, chamomile, savory, nutmeg,cinnamon, hyssop, caraway, orange, geranium, cade, and bergamot oils,fish oils, glycerol tricaprocaprylate; and mixtures thereof. The naturaloils can also be utilized as emollients.

Natural and synthetic wax conditioning agents can be employed in thecompositions of the invention, including but are not limited to carnaubawax, candelila wax, alfa wax, paraffin wax, ozokerite wax, olive wax,rice wax, hydrogenated jojoba wax, bees wax, modified bees wax, e.g.,cerabellina wax, marine waxes, polyolefin waxes, e.g., polyethylene wax;and mixtures thereof.

Liquid polyolefin conditioning oils can be used in the compositions ofthe present invention. The liquid polyolefin conditioning agents aretypically poly-α-olefins that have been hydrogenated. Polyolefins foruse herein can be prepared by the polymerization of C₄ to about C₁₄olefinic monomers. Non-limiting examples of olefinic monomers for use inpreparing the polyolefin liquids herein include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, branched chain isomers such as 4-methyl-1-pentene, andmixtures thereof. In one aspect of the invention, hydrogenated α-olefinmonomers include, but are not limited to: 1-hexene to 1-hexadecenes,1-octene to 1-tetradecene, and mixtures thereof.

Fluorinated or perfluorinated oils are also contemplated within thescope of the present invention. Fluorinated oils includeperfluoropolyethers described in European Patent 0 486 135 and thefluorohydrocarbon compounds described in WO 93/11103. The fluoridatedoils may also be fluorocarbons such as fluoramines, e.g.,perfluorotributylamine, fluoridated hydrocarbons, such asperfluorodecahydronaphthalene, fluoroesters, and fluoroethers.

Other suitable organic conditioners for use as the conditioning agent inthe compositions of the present invention include, but are not limitedto, fatty esters having at least 10 carbon atoms. These fatty estersinclude esters derived from fatty acids or alcohols (e.g., mono-esters,polyhydric alcohol esters, and di- and tri-carboxylic acid esters). Thefatty esters hereof may include or have covalently bonded thereto othercompatible functionalities, such as amides and alkoxy moieties (e.g.,ethoxy or ether linkages, etc.).

Exemplary fatty esters include, but are not limited to isopropylisostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate,isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate,decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryllactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate,oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate.

Other fatty esters suitable for use in the compositions of the presentinvention are mono-carboxylic acid esters of the general formulaR⁵⁰C(O)OR⁵¹, wherein R⁵⁰ and R⁵¹ are alkyl or alkenyl radicals, and thesum of carbon atoms in R⁵⁰ and R⁵¹ is at least 10 in one aspect, and atleast 22 in another aspect of the invention.

Still other fatty esters suitable for use in the compositions of thepresent invention are di- and tri-alkyl and alkenyl esters of carboxylicacids, such as esters of C₄-C₈ dicarboxylic acids (e.g., C₁-C₂₂ esters,preferably C_(1-C6), of succinic acid, glutaric acid, adipic acid).Specific non-limiting examples of di- and tri-alkyl and alkenyl estersof carboxylic acids include isocetyl stearyol stearate, diisopropyladipate, and tristearyl citrate.

Other fatty esters suitable for use in the compositions of the presentinvention are those known as polyhydric alcohol esters. Such polyhydricalcohol esters include alkylene glycol esters, such as ethylene glycolmono and di-fatty acid esters, diethylene glycol mono- and di-fatty acidesters, polyethylene glycol mono- and di-fatty acid esters, propyleneglycol mono- and di-fatty acid esters, polypropylene glycol monooleate,polypropylene glycol 2000 monostearate, ethoxylated propylene glycolmonostearate, glyceryl mono- and di-fatty acid esters, polyglycerolpoly-fatty acid esters, ethoxylated glyceryl monostearate, 1,3-butyleneglycol monostearate, 1,3-butylene glycol distearate, polyoxyethylenepolyol fatty acid ester, sorbitan fatty acid esters, and polyoxyethylenesorbitan fatty acid esters.

Specific non-limiting examples of suitable synthetic fatty esters foruse in the personal cleansing compositions of the present inventioninclude: P-43 (C₈-C₁₀ triester of trimethylolpropane), MCP-684(tetraester of 3,3 diethanol-1,5 pentadiol), MCP 121 (C₈-C₁₀ diester ofadipic acid), all of which are available from ExxonMobil ChemicalCompany.

Other oily material conditioning agents that are useful in combinationwith the polymers of the present invention include, for example,acetylated lanolin alcohols; lanolin alcohol concentrates; esters oflanolin fatty acids such as the isopropyl esters of lanolin fatty acid;polyol fatty acids; ethoxylated alcohols, such as ethoxylate and castoroils; sterols; sterol esters; sterol ethoxylates; and like materials.

Cationic polymers are also useful as conditioning agents alone or incombination with the other conditioning agents described herein.Suitable cationic polymers can be synthetically derived or modifiednatural polymers such as the cationically modified polysaccharides.While several of the cationic polymers listed herein as suitableconditioning agents are duplicative of those described above for uses inother applications, those of skill in the art will recognize that manypolymers serve multiple functions.

Representative cationic polymer conditioners include but are not limitedto homopolymers and copolymers derived from free radically polymerizableacrylic or methacrylic ester or amide monomers. The copolymers cancontain one or more units derived from acrylamides, methacrylamides,diacetone acrylamides, acrylic or methacrylic acids or their esters,vinyllactams such as vinyl pyrrolidone or vinyl caprolactam, and vinylesters. Exemplary polymers include copolymers of acrylamide and dimethylamino ethyl methacrylate quaternized with dimethyl sulfate or with analkyl halide; copolymers of acrylamide and methacryloyl oxyethyltrimethyl ammonium chloride; the copolymer of acrylamide andmethacryloyl oxyethyl trimethyl ammonium methosulfate; copolymers ofvinyl pyrrolidone/dialkylaminoalkyl acrylate or methacrylate, optionallyquaternized, such as the products sold under the name GAFQUAT™ byInternational Specialty Products; the dimethyl amino ethylmethacrylate/vinyl caprolactam/vinyl pyrrolidone terpolymers, such asthe product sold under the name GAFFIX™ VC 713 by InternationalSpecialty Products; the vinyl pyrrolidone/methacrylamidopropyldimethylamine copolymer, marketed under the name STYLEZE™ CC 10available from International Specialty Products; and the vinylpyrrolidone/quaternized dimethyl amino propyl methacrylamide copolymerssuch as the product sold under the name GAFQUAT™ HS100 by InternationalSpecialty Products.

Cationic conditioner agents can also be selected from the quaternarypolymers of vinyl pyrrolidone and vinyl imidazole such as the productssold under the trade name Luviquat® (product designation FC 905, FC 550,and FC 370) by BASF. Other cationic polymer conditioners that can beused in the compositions of the invention include polyalkyleneiminessuch as polyethyleneimines, polymers containing vinyl pyridine or vinylpyridinium units, condensates of polyamines and epichlorhydrins,quaternary polysaccharides, quaternary polyurethanes, and quaternaryderivatives of chitin.

Other non-limiting examples of quaternary ammonium compounds useful ascationic conditioners in the present invention include acetamidopropyltrimonium chloride, behenamidopropyl dimethylamine, behenamidopropylethyldimonium ethosulfate, behentrimonium chloride, cetethylmorpholinium ethosulfate, cetrimonium chloride, cocoamidopropylethyldimonium ethosulfate, dicetyldimonium chloride, dimethiconehydroxypropyl trimonium chloride, hydroxyethyl behenamidopropyl dimoniumchloride, quaternium-26, quaternium-27, quaternium-53, quaternium-63,quaternium-70, quaternium-72, quaternium-76 hydrolyzed collagen, PPG-9diethylmonium chloride, PPG-25 diethylmonium chloride, PPG-40diethylmonium chloride, stearalkonium chloride, stearamidopropyl ethyldimonium ethosulfate, steardimonium hydroxypropyl hydrolyzed wheatprotein, steardimonium hydroxypropyl hydrolyzed collagen, wheatgermamidopropalkonium chloride, wheat germamidopropyl ethyldimoniumethosulfate, polymers and copolymers of dimethyl diallyl ammoniumchloride, such as Polyquaternium-4, Polyquaternium-6, Polyquaternium-7,Polyquaternium-10, Polyquaternium-11, Polyquarternium-16,Polyquaternium-22, Polyquaternium-24, Polyquaternium-28,Polyquaternium-29, Polyquaternium-32, Polyquaternium-33,Polyquaternium-35, Polyquaternium-37, Polyquaternium-39,Polyquaternium-44, Polyquaternium-46, Polyquaternium-47,Polyquaternium-52, Polyquaternium-53, Polyquarternium-55,Polyquaternium-59, Polyquaternium-61, Polyquaternium-64,Polyquaternium-65, Polyquaternium-67, Polyquaternium-69,Polyquaternium-70, Polyquaternium-71, Polyquaternium-72,Polyquaternium-73, Polyquaternium-74, Polyquaternium-76,Polyquaternium-77, Polyquaternium-78, Polyquaternium-79,Polyquaternium-80, Polyquaternium-81, Polyquaternium-82,Polyquaternium-84, Polyquaternium-85, Polyquaternium-87,PEG-2-cocomonium chloride.

As discussed above, numerous ingredients are known in the art asconditioning agents for hair or skin. In addition to those discussed,other non-limiting examples include PCA (DL-pyrrolidone carboxylic acid)and its salts, such as lysine PCA, aluminum PCA, copper PCA, chitosanPCA, and the like, allantoin; urea; hyaluronic acid and its salts;ceramides; sorbic acid and its salts; sugars and starches andderivatives thereof; lactamide MEA; and the like.

In another embodiment of the invention, the cationically andhydrophilically modified Cassia polymers of the invention can beformulated in combination with one or more auxiliary rheology modifiersand thickeners. Suitable rheology modifiers and thickeners includesynthetic and semi-synthetic rheology modifiers. Exemplary syntheticrheology modifiers include acrylic based polymers and copolymers. Oneclass of acrylic based rheology modifiers are the carboxyl functionalalkali-swellable and alkali-soluble thickeners (ASTs) produced by thefree-radical polymerization of acrylic acid alone or in combination withother ethylenically unsaturated monomers. The polymers can besynthesized by solvent/precipitation as well as emulsion polymerizationtechniques. Exemplary synthetic rheology modifiers of this class includehomopolymers of acrylic acid or methacrylic acid and copolymerspolymerized from one or more monomers of acrylic acid, substitutedacrylic acid, and salts and C₁-C₃₀ alkyl esters of acrylic acid andsubstituted acrylic acid. As defined herein, the substituted acrylicacid contains a substituent positioned on the alpha and/or beta carbonatom of the molecule wherein the substituent is preferably andindependently selected from C₁₋₄ alkyl, —CN, and —COOH. Optionally,other ethylenically unsaturated monomers such as, for example, styrene,vinyl acetate, ethylene, butadiene, acrylonitrile, as well as mixturesthereof can be copolymerized into the backbone. The foregoing polymersare optionally crosslinked by a monomer that contains two or moremoieties that contain ethylenic unsaturation. In one aspect, thecrosslinker is selected from a polyalkenyl polyether of a polyhydricalcohol containing at least two alkenyl ether groups per molecule. OtherExemplary crosslinkers are selected from allyl ethers of sucrose andallyl ethers of pentaerythritol, and mixtures thereof. These polymersare more fully described in U.S. Pat. No. 5,087,445; U.S. Pat. No.4,509,949; and U.S. Pat. No. 2,798,053 herein incorporated by reference.

In one embodiment, the AST rheology modifier or thickener is acrosslinked homopolymer polymerized from acrylic acid or methacrylicacid and is generally referred to under the INCI name of Carbomer.Commercially available Carbomers include Carbopol® polymers 934, 940,941, 956, 980 and 996 available from Lubrizol Advanced Materials, Inc.In another embodiment the AST rheology modifier is selected from acrosslinked copolymer polymerized from a first monomer selected from oneor more monomers of (meth)acrylic acid, substituted acrylic acid, andsalts of (meth)acrylic acid and substituted acrylic acid and a secondmonomer selected from one or more C₁-C₅ alkyl acrylate esters of(meth)acrylic acid. These polymers are designated under the INCI name ofAcrylates Copolymer. Acrylates Copolymers are commercially availableunder the trade names Aculyn® 33 from Rohm and Haas and Carbopol® AquaSF-1 from Lubrizol Advanced Materials, Inc. In a further aspect therheology modifier is selected from a crosslinked copolymer polymerizedfrom a first monomer selected from one or more monomers of acrylic acid,substituted acrylic acid, salts of acrylic acid and salts of substitutedacrylic acid and a second monomer selected from one or more C₁₀-C₃₀alkyl acrylate esters of acrylic acid or methacrylic acid. In oneaspect, the monomers can be polymerized in the presence of a stericstabilizer such as disclosed in U.S. Pat. No. 5,288,814 which is hereinincorporated by reference. Some of the forgoing polymers are designatedunder INCI nomenclature as Acrylates/C10-30 Alkyl Acrylate Crosspolymerand are commercially available under the trade names Carbopol® 1342 and1382, Carbopol® Ultrez 20 and 21, Carbopol® ETD 2020 and Pemulen® TR-1and TR-2 from Lubrizol Advanced Materials, Inc. Any vinyl or acrylicbased rheology modifiers are suitable.

Another class of synthetic rheology modifiers and thickeners suitablefor use in the present invention includes hydrophobically modified ASTscommonly referred to as hydrophobically modified alkali-swellable andalkali-soluble emulsion (HASE) polymers. Typical HASE polymers are freeradical addition polymers polymerized from pH sensitive or hydrophilicmonomers (e.g., acrylic acid and/or methacrylic acid), hydrophobicmonomers (e.g., C₁-C₃₀ alkyl esters of acrylic acid and/or methacrylicacid, acrylonitrile, styrene), an “associative monomer”, and an optionalcrosslinking monomer. The associative monomer comprises an ethylenicallyunsaturated polymerizable end group, a non-ionic hydrophilic midsectionthat is terminated by a hydrophobic end group. The non-ionic hydrophilicmidsection comprises a polyoxyalkylene group, e.g., polyethylene oxide,polypropylene oxide, or mixtures of polyethylene oxide/polypropyleneoxide segments. The terminal hydrophobic end group is typically a C₈-C₄₀aliphatic moiety. Exemplary aliphatic moieties are selected from linearand branched alkyl substituents, linear and branched alkenylsubstituents, carbocyclic substituents, aryl substituents, aralkylsubstituents, arylalkyl substituents, and alkylaryl substituents. In oneaspect, associative monomers can be prepared by the condensation (e.g.,esterification or etherification) of a polyethoxylated and/orpolypropoxylated aliphatic alcohol (typically containing a branched orunbranched C₈-C₄₀ aliphatic moiety) with an ethylenically unsaturatedmonomer containing a carboxylic acid group (e.g., acrylic acid,methacrylic acid), an unsaturated cyclic anhydride monomer (e.g., maleicanhydride, itaconic anhydride, citraconic anhydride), amonoethylenically unsaturated monoisocyanate (e.g.,α,α-dimethyl-m-isopropenyl benzyl isocyanate) or an ethylenicallyunsaturated monomer containing a hydroxyl group (e.g., vinyl alcohol,allyl alcohol). Polyethoxylated and/or polypropoxylated aliphaticalcohols are ethylene oxide and/or propylene oxide adducts of amonoalcohol containing the C₈-C₄₀ aliphatic moiety. Non-limitingexamples of alcohols containing a C₈-C₄₀ aliphatic moiety are caprylalcohol, iso-octyl alcohol (2-ethyl hexanol), pelargonic alcohol(1-nonanol), decyl alcohol, lauryl alcohol, myristyl alcohol, cetylalcohol, cetyl alcohol, cetearyl alcohol (mixture of C₁₆-C₁₈monoalcohols), stearyl alcohol, isostearyl alcohol, elaidyl alcohol,oleyl alcohol, arachidyl alcohol, behenyl alcohol, lignoceryl alcohol,ceryl alcohol, montanyl alcohol, melissyl, lacceryl alcohol, geddylalcohol, and C₂-C₂₀ alkyl substituted phenols (e.g., nonyl phenol), andthe like.

Exemplary HASE polymers are disclosed in U.S. Pat. Nos. 3,657,175;4,384,096; 4,464,524; 4,801,671; and 5,292,843, which are hereinincorporated by reference. In addition, an extensive review of HASEpolymers is found in Gregory D. Shay, Chapter 25, “Alkali-Swellable andAlkali-Soluble Thickener Technology A Review”, Polymers in AqueousMedia—Performance Through Association, Advances in Chemistry Series 223,J. Edward Glass (ed.), ACS, pp. 457-494, Division Polymeric Materials,Washington, D.C. (1989), the relevant disclosures of which areincorporated herein by reference. The HASE polymers are commerciallyavailable from Rohm & Haas under the trade designations Aculyn® 22 (INCIName: Acrylates/Steareth-20 Methacrylate Copolymer), Aculyn® 44 (INCIName: PEG-150/Decyl Alcohol/SMDI Copolymer), Aculyn 46® (INCI Name:PEG-150/Stearyl Alcohol/SMDI Copolymer), and Aculyn® 88 (INCI Name:Acrylates/Steareth-20 Methacrylate Crosspolymer).

Another class of synthetic and semi-synthetic rheology modifiers andthickeners suitable for use in the present invention includescationically modified acrylic polymers and copolymers and cationicallymodified cellulose ethers. The acrylic polymers and copolymers andcellulose ethers are cationically modified via quaternization. For theacrylic polymers and copolymers, quaternization can occur bypolymerizing a quaternized monomer into the acrylic polymer backbone orby post functionalizing the acrylic polymer with a quaternizing agent.An exemplary quaternary acrylic polymer is designated under INCInomenclature as Polyquaternium-37 and is commercially available underthe trade names Synthalen CR21 and Synthalen CN, from 3V Inc. Thequaternized celluloses are prepared by post functionalizing the desiredcellulosic backbone (e.g., hydroxyethyl cellulose) with a quaternizingagent such as a quaternary ammonium salt (e.g., diallyldimethyl ammoniumchloride, trimethyl ammonium chloride substituted epoxide). Exemplaryquaternary cellulosic polymers are designated under the INCI namesPolyquaternium-4, Polyquaternium-10, and Polyquaternium-67.

In another embodiment, acid swellable associative polymers can be usedwith the cationically and hydrophilically modified polymers of thepresent invention. Such polymers generally have cationic and associativecharacteristics. These polymers are free radical addition polymerspolymerized from a monomer mixture comprising an acid sensitive aminosubstituted hydrophilic monomer (e.g., dialkylamino alkyl(meth)acrylates or (meth)acrylamides), an associative monomer (definedhereinabove), a lower alkyl (meth)acrylate or other free radicallypolymerizable comonomers selected from hydroxyalkyl esters of(meth)acrylic acid, vinyl and/or allyl ethers of polyethylene glycol,vinyl and/or allyl ethers of polypropylene glycol, vinyl and/or allylethers of polyethylene glycol/polypropylene glycol, polyethylene glycolesters of (meth)acrylic acid, polypropylene glycol esters of(meth)acrylic acid, polyethylene glycol/polypropylene glycol esters of(meth)acrylic acid), and combinations thereof. These polymers canoptionally be crosslinked. By acid sensitive is meant that the aminosubstituent becomes cationic at low pH values, typically ranging fromabout 0.5 to about 6.5. Exemplary acid swellable associative polymersare commercially available under the trade name Structure® Plus (INCIName: Acrylates/Aminoacrylates/C10-C30 Alkyl PEG-20 Itaconate) from AkzoNobel, and Carbopol® Aqua CC (INCI Name: Polyacrylates-1 Crosspolymer)from Lubrizol Advanced Materials, Inc. In one aspect, the acid swellablepolymer is a copolymer of one or more C₁-C₅ alkyl esters of(meth)acrylic acid, C₁-C₄ dialkylamino C₁-C₆ alkyl methacrylate,PEG/PPG-30/5 alkyl ether, PEG 20-25 C₁₀-C₃₀ alkyl ether methacrylate,hydroxy C₂-C₆ alkyl methacrylate crosslinked with ethylene glycoldimethacrylate. Other useful acid swellable associative polymers aredisclosed in U.S. Pat. No. 7,378,479, the disclosure of which is hereinincorporated by reference.

Hydrophobically modified alkoxylated methyl glucoside, such as, forexample, PEG-120 Methyl Glucose Dioleate, PEG-120 Methyl GlucoseTrioleate, and PEG-20 Methyl Glucose Sesquistearate, available fromLubrizol Advanced Materials, Inc., under the trade names, Glucamate®DOE-120, Glucamate™ LT, and Glucamate™ SSE-20, respectively, are alsosuitable rheology modifiers.

Polysaccharides obtained from tree and shrub exudates, such as gumArabic, gum gahatti, and gum tragacanth, as well as pectin; seaweedextracts, such as alginates and carrageenans; algae extracts, such asagar; microbial polysaccharides, such as xanthan, gellan, and wellan;cellulose ethers, such as ethylhexylethylcellulose,hydroxybutylmethylcellulose, hydroxyethylmethylcellulose,hydroxypropylmethylcellulose, methylcellulose, carboxymethylcellulose,hydroxyethylcellulose, and hydroxypropylcellulose; polygalactomannans,such as fenugreek gum, cassia gum, locust bean gum, tara gum, and guargum; starches, such as corn starch, tapioca starch, rice starch, wheatstarch, potato starch and sorghum starch can also be employed in thecompositions herein as suitable thickeners and rheology modifiers.

Other rheology modifiers suitable for use in the personal carecompositions of the invention are disclosed in U.S. Pat. No. 7,205,271the disclosure of which is herein incorporated by reference.

The rheology modifiers set forth above, when employed, can be used aloneor in combination and typically are used in an amount ranging from about0.1 wt. % to about 5 wt. % in one aspect, from about 0.3 wt. % to about3 wt. % in another aspect, and from about 0.5 wt. % to about 2 wt. % infurther aspect, based on the total weight of the personal carecompositions of the present invention.

Where applicable, any known aerosol propellant can be utilized todeliver the personal care, home care, health care and institutional carecompositions containing the cationically and hydrophilically modifiedCassia polymers of the present invention in combination with one or moreof the foregoing active ingredients and/or with the one or moreadditives and/or adjuvants, conventionally or popularly included inpersonal care, health care, home care, and institutional care productsdiscussed above. Exemplary propellants include, but are not limited to,lower boiling hydrocarbons such as C₃-C₆ straight and branched chainhydrocarbons. Exemplary hydrocarbon propellants include propane, butane,isobutene, and mixtures thereof. Other suitable propellants includeethers, such as, dimethyl ether, hydrofluorocarbons, such as,1,1-difluoroethane, and compressed gasses, such as air and carbondioxide. These compositions can contain from about 0.5 to about 60 wt. %of the propellant in one embodiment and from about 0.5 to about 35 wt. %in another embodiment, based on the total weight of the composition.

While overlapping weight ranges for the various components andingredients that can be contained in the compositions of the inventionhave been expressed for selected embodiments and aspects of theinvention, it should be readily apparent that the specific amount ofeach component in the disclosed personal care, home care, health care,and institutional care compositions will be selected from its disclosedrange such that the amount of each component is adjusted such that thesum of all components in the composition will total 100 wt. %. Theamounts employed will vary with the purpose and character of the desiredproduct and can be readily determined by one skilled in the formulationarts and from the literature.

It is also to be recognized that the choice and amount of ingredients inpersonal care, home care, health care and institutional carecompositions that include the cationically and hydrophilically modifiedCassia polymers of the invention can vary depending on the intendedproduct and its function, as is well known to those skilled in theformulation arts. An extensive listing of ingredients and theirconventional functions and product categories have been disclosed andcan be readily ascertained from the literature, some of which can servemore than one function.

This invention is illustrated by the following examples that are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of the invention or the manner in which it can be practiced.Unless specifically indicated otherwise, parts and percentages are givenby weight.

Methods Monosaccharide Content

It is well understood by those skilled in the art that naturalgalactomannans, even when obtained from a single source, will containvarying ranges of mannose to galactose ratios. Accordingly, thesemannose to galactose ratios are reported as average ratios. Themonosaccharide content of Cassia gum can be determined using a methodadapted from Englyst et al. (“Determination of Dietary Fibre asNon-Starch Polysaccharides by Gas-Liquid Chromatography.” Analyst (117),November 1992, pp. 1707-1714. In this method Cassia seed endosperm (300mg), sand (300 mg), and acetone (40 mL) are stirred together for 30minutes. The acetone (containing the fat fraction) is decanted and theremaining sample is dried in an 80° C. bath. Polysaccharide hydrolysisis performed using sulfuric acid (12 M, 5 mL) in a 35° C. bath withmagnetic stirring for 1 hr. Then, water (25 mL) is added, and hydrolysisis allowed to continue for another hour with stirring at a temperatureof 100° C. bath. The sample vial is cooled to room temperature in tapwater. The hydrolysate solution (3 mL) is transferred to a new vial, andan ammonia solution (12.5 M, 1 mL) is added and mixed briefly (If the pHof the hydrolysate solution is not greater than 7, a little more ammoniasolution is added). For the reduction of the monosaccharides in thehydrolysate, octan-2-ol (5 μL) and an ammonia-sodium tetrahydroboratesolution (200 μL of a solution of 1.2 g sodium tetrahydroborate in 6 mLof 12.5M aqueous ammonia) are stirred together in a 40° C. bath 30minutes, after which glacial acetic acid (400 μL) is mixed in toneutralize the solution. The reduction solution (500 μL) is transferredto new glass vial and acetylated by adding 1-methyl imidazole (500 μL)and acetic anhydride (5 mL) and mixing for 10 minutes. Ethanol (900 μL)is added and mixing is continued for another 5 minutes, followed byadding deionized water (10 mL) and continued mixing for another 5minutes. Bromophenol blue (500 μL) is added to the mixture. The vial isplaced in an ice bath and aqueous potassium hydroxide (5 mL of a 7.5 Msolution in water) is mixed into the vial. After 2 minutes, another 5 mLof the potassium hydroxide solution is placed into the vial and mixed.After 15 minutes, or when liquid separation occurs, the clear upperphase (ethyl acetate) is collected, leaving behind a lower blue aqueousphase.

The ethyl acetate phase is diluted in methanol (4× by volume) andinjected into a Hewlett Packard 6890 gas chromatograph equipped with aflame ionization detector. The components of the sample are separated bya 30 m by 0.32 mm fused silica column coated with 0.5 μm RTX-50stationary phase. The GC oven is maintained at 225° C. isothermallythroughout the run. Inlet and detector temperatures are maintained at275° C. Mannitol-hexaacetate is detected at 12.1-12.2 minutes,sorbitol-hexaacetate is detected at 12.4-12.5 minutes, andgalactitol-hexaacetate is detected at 12.9-13.0 minutes. Utilizing thisprocedure the mannose: galactose ratios of tested galactomannans is asfollows:

Galactomannan Mannose:Galatose Ratio Galactose (wt. %) Cassia Gum 8.5 11Guar Gum 1.5 40 Tara Gum 3.0 25 Locust Bean Gum 3.2 24

Molecular Weight

For dissolution of each gum sample, 250 mg of gum is weighed anddispersed into 50 ml of DI water. This slurry/solution is then de-gassedby bubbling nitrogen gas through the mixture for 30 minutes and then isfollowed by refluxing at 115° C. for 2 hours. The sample is then cooledto 0° C. at which time 1.5 g of NaOH and 1.0 g urea are added withstirring. Once all of the salts are dissolved, the sample is placed in afreezer at −12° C. and frozen solid overnight. The following day thesample is warmed to room temperature in a water bath and is fullythawed. It is then placed back into the freezer and frozen solid againovernight. Each sample is subjected to a total of 3 freeze/thaw cyclesbefore being neutralized to pH 7 with approx. 2.2 mL of glacial aceticacid. This process renders fully soluble viscous solutions. The weightaverage molecular weights and number average molecular weightsreferenced herein are measured by low angle light scattering at roomtemperature using a 2× PLaquagel OH-Mixed-H 8 μm 300×7.5 mm column at aconcentration of approximately 0.9 mg/mL in a buffer solution of 0.2MNaNO₃, 0.01M NaH₂PO₄ at pH-7 as the eluent at a flow rate of 1 mL/min.(Each sample was pre-filtered through a 0.5 μm syringe filter.) Thedetectors used were a PL-GPC 50 Plus Refractive Index Detector with a PD2020 Light Scattering Detector. PL-Cirrus software is used to analyzethe results and to calculate M_(n) and M_(w) of the polygalactomannan.

Degree of Substitution

The degree of hydrophilic substitution (DS_(hydrophile)) can bedetermined by applying the Zeisel method (K. L. Hodges, W. E. Kester, D.L. Wiederrich, and J. A. Grover, Determination of Alkoxyl Substitutionin Cellulose Ethers by Zeisel-Gas Chromatography, Analytical Chemistry,Vol. 51 (No. 13), November (1979) pp. 2172-2176). Upon exposure ofhydriodic acid to the derivatized Cassia, alkyl iodide will be liberatedin an amount equivalent to the amount of alkylene oxide repeat unitspresent in the derivatized Cassia. Dividing by the average degree ofpolymerization of the hydrophilic substituent, dp, will yieldDS_(hydrophile) (DS_(hydrophile)=mol_(alkyl iodide)/dp).

In the case where the cationic substituent is appended on thegalactomannan in a first step and the hydrophilic substituent isappended in a second step, the DS_(hydrophile) can also be determinedfrom the reduction in the product's nitrogen weight fraction, since thehydrophilic substituent contains a different nitrogen composition fromthe previous step's cationic galactomannan. DS_(cat) is determined fromthe wt. % nitrogen determined in the first step DS_(cat)=%N_(step1)×(MW_(anhydrous saccharide)) (MW_(N)−% N_(step1)×MW_(cat)).Then, DS_(hydrophile)=(% N_(step2)×MW_(anhydrous saccharide unit)+%N_(step2)×DS_(cat)×MW_(cat)−% N_(step2)×MW_(N))/(MW_(N)×b−%N_(step2)×MW_(hydrophile)), where b is the average number of nitrogenequivalents contained in the hydrophilic substituent.

Fixative Properties High Humidity Spiral Curl Retention (HHSCR) Test

The resistance of a polymer fixative composition to high humidity (about90% Relative Humidity (RH)) is an important property for fixativeapplications and is measured by its ability to hold a curl set on hairafter absorption of water from the applied composition and from thesurrounding atmosphere employing the well known technique commonlyreferred to as high humidity spiral curl retention (HHSCR). Descriptionsof the HHSCR methodology are readily found in the cosmetic literature(see, for example, Ch. 30, Harry's Cosmeticology, 8th Ed., M. J. Rieger,Ph.D. (ed.), pp. 666-667, Chemical Publishing Co., Inc., New York, N.Y.,2000, and Diaz et al., J. Soc. Cosmet. Chem., 34, pp. 205-212, July1983, the relevant disclosures of each are incorporated herein byreference.

Tresses of commercially blended untreated (virgin) human hair areprepared employing natural brown or black color European hair suppliedby International Hair Importers and Products Inc., New York. The tressesused for this test are comprised of European brown hair, weighing 0.5 g,7 inches long and 0.5 inches wide with a sewn/glued flat binding and areindividually wrapped (from root to tip) around a spiral perm rod (CyberSprials™ large spiral curling rods, 8 mm inner diameter, 13.5 mm outerdiameter, 162 mm length, American Discount Beauty Supply, 269 SouthBeverly Drive #250, Beverly Hills, Calif.). Prior to use, each tress iswashed with a dilute aqueous solution of sodium lauryl sulfate (10% SLS)followed by thorough rinsing with de-ionized water at ambient roomtemperature. The tresses are dried by towel blotting. The initialextended length of the hair tress (L_(e)) is measured and recorded. 0.1g of the polymer fixative compositions to be evaluated is applied toeach hair tress. The polymer fixative composition to be evaluated isapplied to the hair tress and distributed uniformly from the rootportion of the hair to tip portion. The treated hair tress is wrappedaround a spiral hair curler and dried for 12 hours at ambient roomtemperature of about 21 to 23° C. and controlled relative humidity(50%). After drying, the curler is carefully removed, leaving the hairtress styled into a spiral curl, the initial length of the hair curl(L_(i)) is measured and recorded. The curled hair tress is verticallyhung in a humidity chamber set at a temperature of about 23° C. and arelative humidity level of 90%.

High humidity spiral curl retention is determined by measuring thelength of the hair curl as the curl relaxes (L_(i)). The change in curllength (droop) is periodically measured at selected intervals and ismonitored over a period of 24 hours. An initial measurement is taken attime zero, followed by measurements at 0.25 hour intervals for the firsthour of exposure, followed by measurements taken at 0.5 hour intervalsfor the second hour of exposure, followed by measurements taken at 1.0hour intervals for the remaining 22 hours of exposure. The followingequation is used to calculate percent curl retention, relative to theinitial curl length (L_(i)) and length of the fully extended hair,before curling (L_(e)):

% Curl Retention=(L _(e) −L _(t) /L _(e) −L _(i).)×100

A curl retention of about 70% or more for a minimum period of about 0.75hours at about 90% RH is a conventional benchmark for good high humidityresistance, and an HHSCR greater than 70% after a period of at leastabout 3 hours is deemed very good to excellent.

Sensory Panel Testing of Conditioning Attributes

Two-in-one shampoo formulations are compared by a trained panel (atleast 3 panelists) for conditioning attributes using a forced choicetest design between two treated hair tresses. Hair tresses treated witha base 2-in-1 shampoo formulation that includes a cationically andhydrophilically modified Cassia polymer of the invention are compared tohair tresses treated with an identical base shampoo formulationcontaining a commercially available cationic polymer. Each panelist isasked to indicate which tress performs better for each of 4 sensoryattributes evaluated in comparing the two test formulations on thetreated hair tresses. The sensory attributes evaluated by the panelinclude (1) ease of wet combing, (2) wet feel (slippery feel or wetconditioned feel), (3) ease of dry combing, and (4) dry feel (soft feelor dry conditioned feel). The test protocol utilizes a matrix design of6 treated tresses (3 replicates for each test formulation). The testmatrix allows for the direct blind comparison of the 3 replicate treatedtresses of formulations containing the cationically and hydrophilicallymodified Cassia polymer of the invention versus 3 replicate treatedtresses treated with comparative formulations. By permutation of the 3replicate treatments for each of the test formulations (invention andcomparative), nine comparisons of paired tresses (invention formulationversus comparative formulation) are possible. The matrix is designedsuch that duplicate evaluations are included from the panel members. Atotal of 36 comparisons are carried out with the matrix design. Astatistical analysis (Z-value calculation of preference of inventionformulations versus comparative formulations) is used to determine thelevel of confidence that the invention formulation is statisticallydifferent (better or worse for the selected sensory attribute) from thecomparison formulation.

Hair Tress Preparation Procedure for Sensory Panel Testing

Hair tresses (Caucasian brown hair or Caucasian bleached hair purchasedfrom International Hair Importers, Inc.) weighing 2.5 g (dry wt.) areprewashed with a stripping shampoo (surfactant iso-propanol mixturecontaining 10 wt. % sodium lauryl sulfate and 10 wt. % iso-propanol) andthoroughly rinsed under warm tap water to remove the shampoo. Excesswater is removed by pinching each tress between the index finger and themiddle finger and gently pulling the tress through the gap of thefingers. The damp tress is placed on top of the weighing dish and 0.5 gof the test shampoo formulation is applied evenly down the length of thehair tress. The shampoo is massaged into the tress from the root to thetip of the hair tress. The tress is then rinsed under warm tap water forapproximately 60 seconds. While rinsing, the tress is combed through itslength at least 20 to 25 times to ensure that all residual shampoo isremoved. The treatment step is repeated a second time for a total of twowashes/rinses.

Clarity Testing

The clarity of a composition containing a cationically andhydrophilically modified Cassia polymer of the invention is measured in% T (transmittance) by a Brinkmann PC 920 colorimeter at least about 24hours after the composition is made. Clarity measurements are takenagainst deionized water (clarity rating of 100 percent).

Turbidity Testing

The turbidity of a composition containing a cationically andhydrophilically modified Cassia polymer of the invention is determinedin Nephelometric Turbidity Units (NTU) employing a Nephelometricturbidity meter with distilled water (NTU=0) as the standard.

Example A

To a reaction vessel 160 g of Cassia gum (containing about 10% moisture)obtained from the endosperm of Cassia tora and Cassia obtusifolia isadded to a solution of 921 g of 44% isopropanol and slurried. To thisslurry, 4.5 g of potassium hydroxide is added and the mixture is heatedat 40° C. for 30 minutes under a nitrogen blanket. 92.8 g of2,3-epoxypropyltrimethyl ammonium chloride (Quab 151 from SKW QuabChemicals Inc, 70%) is then added to the slurry. The reaction slurry isheated to 70° C. and the reaction allowed to proceed at this temperaturefor 3 hours. After cooling to 50° C., the mixture is diluted with 380 gof 99% isopropanol and neutralized to a pH of about 7.0 with glacialacetic acid. The hydroxypropyltrimethyl ammonium chloride Cassia productis filtered, washed once with 380 g of 99% isopropanol, air driedovernight and oven dried at 100° C. for 4 hours to produce 179.3 ofcationically derived Cassia. The final product contains 2.18% wt %nitrogen (DS_(cat) 0.33) on a dry weight basis.

Example 1

To a reaction vessel containing 45.0 g of hydroxypropyltrimethylammonium chloride Cassia prepared in accordance with Example A (excepthaving a nitrogen content of 3.3 wt %) is added a solution of 273 g of44% isopropanol and slurried. To the slurry 0.65 g of 20% sodiumhydroxide is added followed by 13.8 g ofmethoxypoly-ethyleneglycolglycidylether MPEG-GE (molecular weight=600)from Rasching GmbH, Ludwighshafen, Germany. The reaction slurry isstirred at 40° C. for 1 hour under a nitrogen blanket. The slurry isheated to 70° C. and allowed to react at this temperature for 3 hours.After cooling to 50° C., the mixture is neutralized to a pH of about 7.0with glacial acetic acid. The hydrophilically modifiedhydroxypropyltrimethyl ammonium chloride Cassia product is filtered,washed once with 135 g of 99% isopropanol, air dried overnight, and ovendried at 100° C. for 4 hours. The final product contains 2.91 wt. %nitrogen on a dry weight basis; a DS_(cat) of 0.59 and a DS_(hydrophile)of 0.055.

Example 2

To a reaction vessel 330 g of Cassia gum (containing about 10% moisture)obtained from the endosperm of Cassia tora and Cassia obtusifolia isadded to an aqueous solution of 2400 g of 24% isopropanol and slurried.To this slurry, 7.3 g of sodium hydroxide is added under a nitrogenblanket. The slurry is heated to 60° C. and this temperature ismaintained for 3 hours. The Cassia is filtered, washed once with 1500 gof 50% isopropanol, and filtered again. To a reaction vessel 770 g offilter cake (260 g solids) is added to a solution of 1400 g of 60%isopropanol and slurried. To this slurry, 3.2 g of sodium hydroxide isadded under a nitrogen blanket. The slurry is heated to 60° C. and heldat this temperature for 1 hour. Then, 120 g of propylene oxide is thenadded to the slurry. The reaction slurry (at 60° C.) is stirred for 3hours. After 3 hours the reaction mixture was not neutralized. Thehydroxylpropyl Cassia product is filtered, washed once with 960 g of 80%isopropanol, and filtered again. (The resulting dried product had anelemental composition of 43.59% C, 6.34% H, and <0.02% N.) To a reactionvessel 170 g of filter cake (63 g solids) of hydroxylpropyl Cassia isadded to a solution of 330 g of 62% isopropanol and slurried. To thisslurry, 1.5 g of sodium hydroxide is added under a nitrogen blanket.Eighty grams of Quab 151 (2,3-epoxypropyltrimethyl ammonium chloridefrom SKW Quab Chemicals Inc, 70%) is then added to the slurry, and theslurry is heated to 70° C. and then is held at this temperature for 3hours with stirring. After cooling to 50° C., the mixture is neutralizedto a pH of about 7.0 with glacial acetic acid. The product is filtered,washed once with 450 g of 80% isopropanol, air dried overnight and thenoven dried at 100° C. for 4 hours to produce 104 g of cationichydroxypropyl Cassia. The final product contains a molar substitution of0.65 hydroxypropyl functionality as determined by ¹H-NMR as determinedfrom the relative sizes of the hydroxypropyl's methyl peak at 1.2 ppmand the saccharide repeat units' anomeric proton peak approximately 5.1ppm. Knowing the hydroxypropyl MS and the wt. % nitrogen (3.29%), thecationic degrees of substitution is determined to be 0.72. (%N=14DS_(cat)/(MW_(anhydrous saccharide)+MW_(propylene oxide)×MS_(hydroxypropyl)+DS_(cat)×MW_(quab151)))

Example 2A

To a reaction vessel 330 g of Cassia gum (containing about 10% moisture)obtained from the endosperm of Cassia tora and Cassia obtusifolia isadded to an aqueous solution of 2400 g of 24% isopropanol and slurried.To this slurry, 7.3 g of sodium hydroxide is added under a nitrogenblanket. The slurry is heated to 60° C. and this temperature ismaintained for 3 hours. The Cassia is filtered, washed once with 1500 gof 50% isopropanol, and filtered again. To a reaction vessel 770 g offilter cake (260 g solids) is added to a solution of 1300 g of 90%isopropanol and slurried. To this slurry, 49.4 g of sodium hydroxide isadded under a nitrogen blanket. The slurry is then stirred for 1 hour.Then, 110 g of ethylene oxide is then added to the slurry. The reactionslurry is heated to 60° C. and is stirred for 3 hours. After 3 hours thereaction mixture is neutralized with acetic acid. The hydroxylethylCassia product, having a hydroxyethyl molar substitution of 1.2, isfiltered, is re-sluried in 99% isopropanol, is filtered again, and isdried in an oven. To a reaction vessel 30 g of dried of hydroxylethylCassia is added to a solution of 210 g of 62% isopropanol and isslurried. To this slurry, 1.1 g of sodium hydroxide is added under anitrogen blanket. Thirty-five grams of Quab 151(2,3-epoxypropyltrimethyl ammonium chloride from SKW Quab Chemicals Inc,70%) is then added to the slurry, and the slurry is heated to 70° C. andthen is held at this temperature for 3 hours with stirring. Aftercooling to 50° C., the mixture is neutralized to a pH of about 7.0 withglacial acetic acid. Similar methodology as employed in Example 2 isutilized to determine DS_(cat). The product is filtered, washed oncewith 190 g of 80% isopropanol, oven dried at 100° C. for 16 hours. Thecationic hydroxyethyl Cassia contains 2.68 wt. % N, with a DS_(cat) of0.57.

Example 2B

To a reaction vessel 160 g of Cassia gum (containing about 10% moisture)obtained from the endosperm of Cassia tora and Cassia obtusifolia isadded to a solution of 921 g of 44% isopropanol and slurried. To thisslurry, 4.5 g of potassium hydroxide is added and the mixture is heatedat 40° C. for 30 minutes under a nitrogen blanket. 67 g of MPEG-GE(molecular weight=600) is then added. The slurry is heated to 70° C. andallowed to react at this temperature for 3 hours. After cooling to 50°C., the mixture is neutralized to a pH of about 7.0 with glacial aceticacid. The MPEG modified Cassia product is filtered, washed once with 380g of 99% isopropanol, air dried overnight, and oven dried at 100° C. for4 hours. Then, to a reaction vessel containing 45.0 g of the dried MPEGmodified Cassia product a solution of 273 g of 44% isopropanol is addedand slurried. To the slurry, 0.65 g of 20% sodium hydroxide is addedfollowed by 26 g of 2,3-epoxypropyltrimethyl ammonium chloride. Thereaction slurry is heated to 70° C. and the reaction allowed to proceedat this temperature for 3 hours. After cooling to 50° C., the mixture isdiluted with 380 g of 99% isopropanol and neutralized to a pH of about7.0 with glacial acetic acid. The hydroxypropyltrimethyl ammoniumchloride MPEG Cassia product is filtered, washed once with 135 g of 99%isopropanol, air dried overnight and oven dried at 100° C. for 4 hoursto produce a product contains 2.2 wt % nitrogen.

Example 3

The procedure of Example 1 was followed except that 45.0 g ofhydroxypropyltrimethyl ammonium chloride cassia with a nitrogen contentof 2.4 wt % (DS_(cat) 0.37), 1.35 g of 20% sodium hydroxide and 30.9 gof methoxy-polyethyleneglycolglycidylether (molecular weight=600) wereused. The cationically and hydrophilically modified product contains1.87 wt. % nitrogen on a dry weight basis with a DS_(cat) of 0.37 andDS_(hydrophile) of 0.10.

Example 4

Two-in-one conditioning shampoo compositions including the cationicallyand hydrophilically modified Cassia polymer of Example 1 (Formulation A)and a commercially available cationic guar polymer (Formulation B) areformulated with the components set forth in Table 1.

TABLE 1 Formulation A Formulation B Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 1 0.25— Guar Hydroxypropyltrimonium — 0.25 Chloride (DS_(cat) 0.21) Jaguar ™C-13S (Rhodia) Silicone Emulsion (DC 1352) 2 2 (Dow Corning) D.I. Waterq.s. to 100 q.s. to 100 Citric Acid (20% aqueous wt./ q.s. to q.s. towt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation A versus Formulation B on Caucasian brownhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Acontaining the cationically and hydrophilically modified Cassia polymerof Example 1 displays statistically significant better wet conditioningproperties in comparison to Formulation B containing the cationic guaron Caucasian brown hair. The results of the panel test indicates thathair tresses treated with Formulation A have better wet combingattributes (99% confidence level), and better wet feel attributes (99%confidence level). No significant statistical differences in the dryconditioning attributes are observed between tresses treated with thetwo formulations with similar dry combing and dry feel.

Example 5

Clear conditioning shampoo compositions including the cationically andhydrophilically modified Cassia polymer of Example 1 (Formulation C) anda commercially available cationic Polyquaternium-10 polymer (FormulationD) are formulated with the components set forth in Table 2.

TABLE 2 Formulation C Formulation D Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 1 0.25— Polyquaternium-10 (DS_(cat) — 0.25 0.33-0.35) Ucare ™ JR400 (AmercolCorporation) D.I. Water q.s. to 100 q.s. to 100 Citric Acid (20% aqueousq.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation C versus Formulation D on Caucasian brownhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Ccontaining the cationically and hydrophilically modified Cassia polymerof Example 1 displays statistically significant better conditioningproperties in comparison to Formulation D containing thePolyquaternium-10 (quaternized hydroxyethylcellulose) on Caucasian brownhair. The results of the panel test indicates that hair tresses treatedwith Formulation C have better wet combing attributes (99% confidencelevel), better wet feel attributes (95% confidence level) and better drycombing attributes (99% confidence level). No significant statisticaldifferences in the dry feel attributes are observed between tressestreated with the two formulations.

Example 6

Clear conditioning shampoo compositions including the cationically andhydrophilically modified Cassia polymer of Example 1 (Formulation E) anda commercially available cationic quaternium polymer (Formulation F) areformulated with the components set forth in Table 3.

TABLE 3 Formulation E Formulation F Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 1 0.25— Polyquaternium-10 (DS_(cat) — 0.25 0.33-0.35) Ucare ™ JR400 (AmercolCorporation) D.I. Water q.s. to 100 q.s. to 100 Citric Acid (20% aqueousq.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation E versus Formulation F on Caucasian bleachedhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Econtaining the cationically and hydrophilically modified Cassia polymerof Example 1 displays statistically significant better conditioningproperties in comparison to Formulation F containing thePolyquaternium-10 (quaternized hydroxyethylcellulose) on Caucasianbleached hair. The results of the panel test indicates that hair tressestreated with Formulation E have better wet combing attributes (99%confidence level), better wet feel attributes (99% confidence level),better dry feel (99% confidence level), and better dry combing (99%confidence level) than Formulation F.

Example 7

Clear conditioning shampoo compositions including the cationically andhydrophilically modified Cassia polymer of Example 3 (Formulation G) anda commercially available cationic Polyquaternium-10 polymer (FormulationH) are formulated with the components set forth in Table 4.

TABLE 4 Formulation G Formulation H Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 3 0.25— Polyquaternium-10 (DS_(cat) — 0.25 0.33-0.35) Ucare ™ JR400 (AmercolCorporation) D.I. Water q.s. to 100 q.s. to 100 Citric Acid (20% aqueousq.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation G versus Formulation H on Caucasian brownhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Gcontaining the cationically and hydrophilically modified Cassia polymerof Example 3 displays statistically significant better wet conditioningproperties in comparison to Formulation H containing thePolyquaternium-10 (quaternized hydroxyethylcellulose) on Caucasian Brownhair. The results of the panel test indicates that hair tresses treatedwith Formulation G have better wet combing attributes (95% confidencelevel), better wet feel attributes (99% confidence level) thanFormulation H. No significant statistical differences in the dryconditioning attributes are observed between tresses treated with thetwo formulations with similar dry combing and dry feel.

Example 8

Clear conditioning shampoo compositions including the cationically andhydrophilically modified Cassia polymer of Example 3 (Formulation K) anda cationically derivatized Cassia polymer synthesized in accordance withExample A but containing 2.4 wt. % nitrogen (DS_(cat) 0.37) and devoidof hydrophilic modification (Formulation L) are formulated with thecomponents set forth in Table 5.

TABLE 5 Formulation K Formulation L Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 3 0.25— Cationic Cassia — 0.25 D.I. Water q.s. to 100 q.s. to 100 Citric Acid(20% aqueous q.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation K versus Formulation L on Caucasian bleachedhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Kcontaining the cationically and hydrophilically modified Cassia polymerof Example 3 displays statistically significant better wet conditioningproperties in comparison to Formulation L containing the cationicallyderivatized Cassia with no hydrophilic modification on CaucasianBleached hair. The results of the panel test indicates that hair tressestreated with Formulation K have better wet combing attributes (95%confidence level) and wet feel attributes (99% confidence level) thanFormulation L.

Example 9

Clear conditioning shampoo compositions including the cationically andhydrophilically modified Cassia polymer of Example 1 (Formulation M) anda cationically derivatized Cassia polymer synthesized in accordance withExample A containing 3.5 wt. % nitrogen (DS_(cat) 0.65) and devoid ofhydrophilic modification (Formulation N) are formulated with thecomponents set forth in Table 6.

TABLE 6 Formulation M Formulation N Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 1 0.25— Cationic Cassia — 0.25 D.I. Water q.s. to 100 q.s. to 100 Citric Acid(20% aqueous q.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0

A sensory panel test is conducted to compare the conditioningperformances of Formulation M versus Formulation N on Caucasian bleachedhair tresses in accordance with the methodology set forth in the SensoryPanel Testing of Conditioning Attributes protocol above. Formulation Mcontaining the cationically and hydrophilically modified Cassia polymerof Example 1 displays statistically significant better wet conditioningproperties in comparison to Formulation N containing the cationicallyderivatized Cassia with no hydrophilic modification. The results of thepanel test indicates that hair tresses treated with Formulation M havebetter wet combing attributes (99% confidence level), and better wetfeel (95% confidence level) than Formulation N on Caucasian bleachedhair.

Example 10

Clear conditioning shampoo formulations are prepared from the componentsset forth in Table 7 including a cationic polymer. The unmodifiedcationic Cassia of Formulation Q is synthesized according to theprocedure set forth in Example A and contains 2.4 wt. % nitrogen(DS_(cat) 0.37).

TABLE 7 Formulation P Formulation Q Component Active (wt %) Active (wt%) Sodium Laureth-3 sulfate 17 17 Sulfochem ™ ES-3 (Lubrizol AdvancedMaterials, Inc.) Cocamidopropylbetaine 3 3 Chembetaine ™ (LubrizolAdvanced Materials, Inc.) Sodium Chloride 1 1 Polymer of Example 3 0.25— Cationic Cassia — 0.25 D.I. Water q.s. to 100 q.s. to 100 Citric Acid(20% aqueous q.s. to q.s. to wt./wt.) pH = 6.0 pH = 6.0 Clarity (% T at420 nm) 94.2 88.7 Turbidity (NTU) 7.7 21.1

Clear shampoo Formulation P containing the cationically andhydrophilically modified Cassia polymer of Example 3 exhibits betterclarity and significantly better turbidity properties than Formulation Qcontaining a non-hydrophilically modified cationic Cassia polymer of asimilar degree of cationic substitution.

Example 11

Fixative compositions are formulated from the cationically andhydrophilically modified polymers of Examples 1 and 3 by dispersing 1wt. % of each polymer in deionized water. The fixative compositions areevaluated for high humidity spiral curl retention as set forth in theHHSCR test methodology set forth above. Two identically preparedfixative compositions utilizing cationically modified cassia (devoid ofhydrophilic modification) prepared in accordance with Example A buthaving DS_(cat) values of 0.62, and 0.37 are utilized for comparison.The results are set forth in Table 8.

TABLE 8 Spiral curl Spiral curl Spiral curl retention at retention atretention at 90% RH-23° C. 3 hours (%) 8 hours (%) 24 hours (%)Hydrophilic modified 68.1 61.7 60.7 cationic cassia of Example 1Comparative to 62.4 61.3 61.3 example 1 (unmodified Cationic cassia 3.5wt % N, DScat = 0.62) Hydrophilic modified 89.5 87.4 87.4 cationiccassia of Example 3 Comparative Example 84.9 84.9 80.6 3 (unmodifiedcationic cassia 2.5 wt % N, DScat = 0.37)

The hydrophilic and cationic modified cassia polymers all displayexcellent high humidity spiral curl retention after 3, 8 and 24 hrs atexposures of 90% relative humidity at 23° C. The results also show thatthe hydrophilic and cationic modified cassia polymers display, in mostcases, better high humidity spiral curl retention compared to cationiccassia without hydrophilic modification of similar cationic chargedensity.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention.

1. A cationically and hydrophilically modified galactomannan having anaverage mannose to galactose ratio of at least 5:1 wherein a portion ofthe hydrogen atoms of the hydroxyl groups present on the galactomannanare substituted with a least one cationic moiety represented by formula(I) and at least one hydrophilic moiety represented by formula (II) asfollows:

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical, and whensubstituted said substituent, independently, is selected from hydroxyland halo; R, independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and—P⁺R³R⁴R⁵X⁻, wherein R³ and R⁴, and R⁵, independently, are selected fromhydrogen and linear and branched C₁-C₂₄ alkyl, and X⁻represents ananion; (R¹—O)_(c) represents a oxyalkylene moiety or a polyoxyalkylenemoiety arranged as a homopolymer, a random copolymer or a blockcopolymer of oxyalkylene units, wherein R¹, independently, is selectedfrom linear and branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups,and c is an integer ranging from about 1 to about 250; R²,independently, is selected from hydrogen, methyl, and AR; and a is 0 or1; b is 0 or 1, subject to the proviso that when a is 0, b is 0, andwhen R² is AR in formula (II), the cationic moiety AR represented byformula (I) is optionally present; and when c is 1, R² is not hydrogen.2. A cationically and hydrophilically modified galactomannan of claim 1wherein AR in formula (I) is represented by the structure:

wherein R³ and R⁴, and R⁵, independently, are selected from C₁-C₅ alkyl,and X is a chloride ion.
 3. A cationically and hydrophilically modifiedgalactomannan of claim 1 wherein at least a portion of R² substituentsin formula (II) are selected from AR.
 4. A cationically andhydrophilically modified galactomannan of claim 3 wherein AR isrepresented by the structure;

wherein R³ and R⁴, and R⁵, and X are as previously defined.
 5. Acationically and hydrophilically modified galactomannan of claim 2wherein in formula (II) a is 1, b is 1, R¹ is —CH₂CH₂—, and R² ismethyl.
 6. A composition comprising: a) a cationically andhydrophilically modified galactomannan having an average mannose togalactose ratio of at least 5:1 wherein a portion of the hydrogen atomsof the hydroxyl groups present on the galactomannan are substituted witha least one cationic moiety represented by formula (I) and at least onehydrophilic moiety represented by formula (II) as follows:

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical, and whensubstituted said substituent, independently, is selected from hydroxyland halo; R, independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and—P⁺R³R⁴R⁵X⁻, wherein R³ and R⁴, and R⁵, independently, are selected fromhydrogen and linear and branched C₁-C₂₄ alkyl, and X⁻ represents ananion; (R¹—O)_(c) represents a oxyalkylene moiety or a polyoxyalkylenemoiety arranged as a homopolymer, a random copolymer or a blockcopolymer of oxyalkylene units, wherein R¹, independently, is selectedfrom linear and branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups,and c is an integer ranging from about 1 to about 250; R²,independently, is selected from hydrogen, methyl, and AR; and a is 0 or1; b is 0 or 1, subject to the proviso that when a is 0, b is 0, andwhen R² is AR in formula (II), the cationic moiety AR represented byformula (I) is optionally present; and when c is 1, R² is not hydrogen;and b) at least one component selected from surfactants, hair and skinconditioning agents, emollients, emulsifiers, rheology modifiers,thickening agents, vitamins, hair growth promoters, self-tanning agents,sunscreens, skin lighteners, anti-aging compounds, anti-wrinklecompounds, anti-cellulite compounds, anti-acne compounds, anti-dandruffagents, anti-inflammatory compounds, analgesics, antiperspirant agents,deodorant agents, hair fixatives, particulates, abrasives, moisturizers,antioxidants, keratolytic agents, anti-static agents, foam boosters,hydrotropes, solubilizing agents, chelating agents, antimicrobialagents, antifungal agents, pH adjusting agents, chelating agents,buffering agents, botanicals, hair colorants, oxidizing agents, reducingagents, hair and skin bleaching agents, pigments, anticaries,anti-tartar agents, anti-plaque agents, solvents; and combinationsthereof.
 7. A composition of claim 6 wherein AR in formula (I) isrepresented by the structure:

wherein R³ and R⁴, and R⁵, independently, are selected from C₁-C₅ alkyl,and X is a chloride ion.
 8. A composition of claim 6 wherein at least aportion of R² substituents in formula (II) are selected from AR.
 9. Acomposition of claim 8 wherein AR is represented by the structure;

wherein R³ and R⁴, and R⁵, and X are as previously defined.
 10. Acomposition of claim 7 wherein in formula (II) a is 1, b is 1, R¹ is—CH₂CH₂—, and R² is methyl.
 11. A composition of claim 6 wherein saidsurfactant is selected from an anionic surfactant, a cationicsurfactant, an amphoteric surfactant, a nonionic surfactant andcombinations thereof.
 12. A composition of claim 6 wherein saidconditioning agent is selected from silicones, organic conditioningoils, natural and synthetic waxes, cationic polymers, and combinationsthereof.
 13. A composition of claim 7 wherein said silicone is selectedfrom silicone fluids, silicone oils, cationic silicones, silicone gums,high refractive silicones, silicone resins, emulsified silicones,dimethicone copolyols; and combinations thereof.
 14. A detersivecomposition comprising: a) a cationically and hydrophilically modifiedgalactomannan having an average mannose to galactose ratio of at least5:1 wherein a portion of the hydrogen atoms of the hydroxyl groupspresent on the galactomannan are substituted with a least one cationicmoiety represented by formula (I) and at least one hydrophilic moietyrepresented by formula (II) as follows:

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical, and whensubstituted said substituent, independently, is selected from hydroxyland halo; R, independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and—P⁺R³R⁴R⁵X⁻, wherein R³ and R⁴, and R⁵, independently, are selected fromhydrogen and linear and branched C₁-C₂₄ alkyl, and X⁻ represents ananion; (R¹—O)_(c) represents a oxyalkylene moiety or a polyoxyalkylenemoiety arranged as a homopolymer, a random copolymer or a blockcopolymer of oxyalkylene units, wherein R¹, independently, is selectedfrom linear and branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups,and c is an integer ranging from about 1 to about 250; R²,independently, is selected from hydrogen, methyl, and AR; and a is 0 or1; b is 0 or 1, subject to the proviso that when a is 0, b is 0, andwhen R² is AR in formula (II), the cationic moiety AR represented byformula (I) is optionally present; and when c is 1, R² is not hydrogen;and b) a surfactant is selected from an anionic surfactant, a cationicsurfactant, an amphoteric surfactant, a nonionic surfactant andcombinations thereof.
 15. A composition of claim 14 wherein AR informula (I) is represented by the structure:

wherein R³ and R⁴, and R⁵, independently, are selected from C₁-C₅ alkyl,and X is a chloride ion.
 16. A composition of claim 14 wherein at leasta portion of R² substituents in formula (II) are selected from AR.
 17. Acomposition of claim 16 wherein AR is represented by the structure;

wherein R³ and R⁴, and R⁵, and X are as previously defined.
 18. Acomposition of claim 15 wherein in formula (II) a is 1, b is 1, R¹ is—CH₂CH₂—, and R² is methyl.
 19. A detersive composition of claim 14further comprising a conditioning agent.
 20. A detersive composition ofclaim 19 wherein said conditioning agent is selected from silicones,organic conditioning oils, natural and synthetic waxes, cationicpolymers, and combinations thereof.
 21. A detersive composition of claim20 wherein said silicone is selected from silicone fluids, siliconeoils, cationic silicones, silicone gums, high refractive silicones,silicone resins, emulsified silicones, dimethicone copolyols; andcombinations thereof.
 22. A detersive composition of claim 20 whereinsaid cationic polymer is selected from a quaternium ammonium compound.23. A hair fixative composition comprising: a) a cationically andhydrophilically modified galactomannan having an average mannose togalactose ratio of at least 5:1 wherein a portion of the hydrogen atomsof the hydroxyl groups present on the galactomannan are substituted witha least one cationic moiety represented by formula (I) and at least onehydrophilic moiety represented by formula (II) as follows:

wherein A, independently, is selected from a divalent linear orbranched, substituted or unsubstituted C₁-C₆ alkylene radical, and whensubstituted said substituent, independently, is selected from hydroxyland halo; R, independently, is selected from —S⁺R³R⁴X⁻, —N⁺R³R⁴R⁵X⁻, and—P⁺R³R⁴R⁵X⁻, wherein R³ and R⁴, and R⁵, independently, are selected fromhydrogen and linear and branched C₁-C₂₄ alkyl, and X⁻ represents ananion; (R¹—O)_(c) represents a oxyalkylene moiety or a polyoxyalkylenemoiety arranged as a homopolymer, a random copolymer or a blockcopolymer of oxyalkylene units, wherein R¹, independently, is selectedfrom linear and branched C₂H₄, C₃H₆, and C₄H₈ divalent alkylene groups,and c is an integer ranging from about 1 to about 250; R²,independently, is selected from hydrogen, methyl, and AR; and a is 0 or1; b is 0 or 1, subject to the proviso that when a is 0, b is 0, andwhen R² is AR in formula (II), the cationic moiety AR represented byformula (I) is optionally present; and when c is 1, R² is not hydrogen;and b) a component selected from a rheology modifier, a surfactant, anauxiliary fixative, a solvent, water, a conditioner, a propellant,neutralizing agent, fragrance, fragrance solubilizer, thickener,preservative, emulsifier, emollient, humectant, colorant, wax, andmixtures thereof.
 24. A composition of claim 23 wherein AR in formula(I) is represented by the structure:

wherein R³ and R⁴, and R⁵, independently, are selected from C₁-C₅ alkyl,and X is a chloride ion.
 25. A composition of claim 23 wherein at leasta portion of R² substituents in formula (II) are selected from AR.
 26. Acomposition of claim 25 wherein AR is represented by the structure;

wherein R³ and R⁴, and R⁵, and X are as previously defined.
 27. Acomposition of claim 24 wherein in formula (II) a is 1, b is 1, R¹ is—CH₂CH₂—, and R² is methyl.
 28. A composition of claim 23 wherein saidconditioner is selected from a silicone, a cationic polymer, andcombinations thereof.
 29. A composition of claim 23 wherein said solventis selected from water, a C₁-C₆ alcohol, a ketone, an ether, andcombinations thereof.
 30. A composition of claim 28 wherein saidcationic polymer is a polyquaternium compound.
 31. A composition ofclaim 29 wherein said propellant is selected from propane, butane,isobutene, dimethyl ether, 1,1-difluoroethane, carbon dioxide, andmixtures thereof.
 32. A composition of claim 1 wherein the averagemannose to galactose ratio of said cationically and hydrophilicallymodified galactomannan ranges from about 5:1 to about 49:1. 33.(canceled)
 34. (canceled)
 35. A composition of claim 1 wherein theaverage mannose to galactose ratio of said cationically andhydrophilically modified galactomannan is about from about 5:1, 6:1,7:1, 8:1, 9:1, and mixtures thereof.
 36. A composition of claim 1wherein the weight of galactose in said cationically and hydrophilicallymodified galactomannan ranges from about 2 wt. % to about 17 wt. % basedon the weight of the galactomannan.
 37. A composition of claim 1 whereinthe cationic degree of substitution ranges from about 0.0001 to about 3.38. (canceled)
 39. (canceled)
 40. A composition of claim 1 wherein thehydrophilic degree of substitution ranges from about 0.0001 to about 3.41.-45. (canceled)
 46. A composition of claim 1 wherein saidgalactomannan is obtained from the endosperm of Cassia tora, Cassiaobtusifolia, and mixtures thereof.
 47. A composition of claim 6 whereinthe average mannose to galactose ratio of said cationically andhydrophilically modified galactomannan ranges from about 5:1 to about49:1.
 48. A composition of claim 6 wherein the average mannose togalactose ratio of said cationically and hydrophilically modifiedgalactomannan is about from about 5:1, 6:1, 7:1, 8:1, 9:1, and mixturesthereof.
 49. A composition of claim 6 wherein the weight of galactose insaid cationically and hydrophilically modified galactomannan ranges fromabout 2 wt. % to about 17 wt. % based on the weight of thegalactomannan.
 50. A composition of claim 6 wherein the cationic degreeof substitution ranges from about 0.0001 to about
 3. 51. A compositionof claim 6 wherein the hydrophilic degree of substitution ranges fromabout 0.0001 to about
 3. 52. A composition of claim 6 wherein saidgalactomannan is obtained from the endosperm of Cassia tora, Cassiaobtusifolia, and mixtures thereof.
 53. A composition of claim 14 whereinthe average mannose to galactose ratio of said cationically andhydrophilically modified galactomannan ranges from about 5:1 to about49:1.
 54. A composition of claim 14 wherein the average mannose togalactose ratio of said cationically and hydrophilically modifiedgalactomannan is about from about 5:1, 6:1, 7:1, 8:1, 9:1, and mixturesthereof.
 55. A composition of claim 14 wherein the weight of galactosein said cationically and hydrophilically modified galactomannan rangesfrom about 2 wt. % to about 17 wt. % based on the weight of thegalactomannan.
 56. A composition of claim 14 wherein the cationic degreeof substitution ranges from about 0.0001 to about
 3. 57. A compositionof claim 14 wherein the hydrophilic degree of substitution ranges fromabout 0.0001 to about
 3. 58. A composition of claim 14 wherein saidgalactomannan is obtained from the endosperm of Cassia tora, Cassiaobtusifolia, and mixtures thereof.
 59. A composition of claim 23 whereinthe average mannose to galactose ratio of said cationically andhydrophilically modified galactomannan ranges from about 5:1 to about49:1.
 60. A composition of claim 23 wherein the average mannose togalactose ratio of said cationically and hydrophilically modifiedgalactomannan is about from about 5:1, 6:1, 7:1, 8:1, 9:1, and mixturesthereof.
 61. A composition of claim 23 wherein the weight of galactosein said cationically and hydrophilically modified galactomannan rangesfrom about 2 wt. % to about 17 wt. % based on the weight of thegalactomannan.
 62. A composition of claim 23 wherein the cationic degreeof substitution ranges from about 0.0001 to about
 3. 63. A compositionof claim 23 wherein the hydrophilic degree of substitution ranges fromabout 0.0001 to about
 3. 64. A composition of claim 23 wherein saidgalactomannan is obtained from the endosperm of Cassia tora, Cassiaobtusifolia, and mixtures thereof.